Solid cleaning composition

ABSTRACT

A solid cleaning composition includes a solidified surfactant blend. The solidified surfactant blend includes (1) at least one metal alkyl ether sulfate having the formula: 
     
       
         
         
             
             
         
       
     
     wherein the first metal is sodium, potassium, magnesium, or calcium, a is 1 or 2, AO is ethylene oxide, propylene oxide, or combinations thereof, x is 0.1 to 3, and y is 11 to 13. The solidified surfactant blend also includes a (2) solid surfactant and optionally (3) polyethylene glycol. Furthermore, (1) and (2) are present in a weight ratio of from 30:70 to 70:30 based on a total weight of the solidified surfactant blend. The solid cleaning composition has non-cohesive powder flow properties as determined using a Brookfield powder flow tester.

CROSS-REFERENCE

This application claims priority under 35 U.S.C. § 119 to ProvisionalApplication U.S. Ser. No. 62/622,300 filed Jan. 26, 2018, hereinincorporated by reference in its entirety including without limitation,the specification, claims, and abstract, as well as any figures, tables,or examples thereof.

FIELD OF THE DISCLOSURE

This disclosure generally relates to a solid cleaning composition. Morespecifically, this disclosure relates to a solid cleaning compositionthat includes a solidified surfactant blend comprising at least onemetal alkyl ether sulfate and a solid surfactant.

BACKGROUND

Some metal alkyl ether sulfate surfactants, such as sodium lauryl ethersulfate, are available only in liquid form. It is desirable to providemetal alkyl ether sulfate surfactants in solid form in order to makesolid cleaning compositions. A challenge in formulating solid productsis incorporating adequate amounts of liquid materials into theformulations without sacrificing the integrity or stability of the solidformulation.

Because some metal alkyl ether sulfate surfactants are only available inliquid form, they cannot easily be incorporated into solid formulations.This has limited the formulation of solid cleaning compositions.Accordingly, there remains opportunity for improvement

SUMMARY OF THE DISCLOSURE

This disclosure provides a solid cleaning composition. The compositionincludes a solidified surfactant blend. The solidified surfactant blendincludes (1) at least one metal alkyl ether sulfate having the formula:

wherein the first metal is sodium, potassium, magnesium, or calcium, ais 1 or 2, AO is ethylene oxide, propylene oxide, or combinationsthereof, x is from 0.1 to 3, and y is from 11 to 13. In a preferredembodiment, the solidified surfactant blend can also include (2) a solidsurfactant and (3) a polyethylene glycol. In embodiments, the solidifiedsurfactant blend further includes an alkalinity source. The at least onemetal alkyl ether sulfate and solid surfactant are generally present ina weight ratio of from 30:70 to 70:30 based on a total weight of thesolidified surfactant blend.

DETAILED DESCRIPTION OF THE DISCLOSURE

This disclosure provides a solid cleaning composition. The compositioncan be used in any application in commercial, industrial, or householdsettings. The composition can be used in a variety of cleaningapplications, including, but not limited to, in laundry, hard surface,ware wash, etc. The cleaning composition is “solid.”

The embodiments of this invention are not limited to particular cleaningapplications, which can vary and are understood by skilled artisans. Itis further to be understood that all terminology used herein is for thepurpose of describing particular embodiments only, and is not intendedto be limiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers defining the range and include each integer within the definedrange. Throughout this disclosure, various aspects of this invention arepresented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges, fractions,and individual numerical values within that range. For example,description of a range such as from 1 to 6 should be considered to havespecifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well asindividual numbers within that range, for example, 1, 2, 3, 4, 5, and 6,and decimals and fractions, for example, 1.2, 3.8, 1½, and 4¾ Thisapplies regardless of the breadth of the range.

Certain terms are first defined so that this disclosure can be morereadily understood. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used without undueexperimentation, the preferred materials and methods are describedherein. The following terminology will be used in accordance with thedefinitions set out below in the following description and the claims.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuringtechniques and equipment, with respect to any quantifiable variable,including, but not limited to, mass, volume, and time. Further, givensolid and liquid handling procedures used in the real world, there iscertain inadvertent error and variation that is likely throughdifferences in the manufacture, source, or purity of the ingredientsused to make the compositions or carry out the methods and the like. Theterm “about” also encompasses amounts that differ due to differentequilibrium conditions for a composition resulting from a particularinitial mixture. The term “about” also encompasses these variations.Whether or not modified by the term “about,” the claims includeequivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

In some embodiments, substituted alkyls can include a heterocyclicgroup. As used herein, the term “heterocyclic group” includes closedring structures analogous to carbocyclic groups in which one or more ofthe carbon atoms in the ring is an element other than carbon, forexample, nitrogen, sulfur or oxygen. Heterocyclic groups may besaturated or unsaturated. Exemplary heterocyclic groups include, but arenot limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan.

An “antiredeposition agent” refers to a compound that helps keepsuspended in water instead of redepositing onto the object beingcleaned. Antiredeposition agents are useful in the present invention toassist in reducing redepositing of the removed soil onto the surfacebeing cleaned.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the components and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods, andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods, and compositions.

The term “laundry” refers to items or articles that are cleaned in alaundry washing machine. In general, laundry refers to any item orarticle made from or including textile materials, woven fabrics,non-woven fabrics, and knitted fabrics. The textile materials caninclude natural or synthetic fibers such as silk fibers, linen fibers,cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylicfibers, acetate fibers, and blends thereof including cotton andpolyester blends. The fibers can be treated or untreated. Exemplarytreated fibers include those treated for flame retardancy. It should beunderstood that the term “linen” is often used to describe certain typesof laundry items including bed sheets, pillow cases, towels, tablelinen, table cloth, bar mops and uniforms. The invention additionallyprovides a composition and method for treating non-laundry articles andsurfaces including hard surfaces such as dishes, glasses, and otherware.

As used herein, the term “polymer” generally includes, but is notlimited to, homopolymers, copolymers, such as for example, block, graft,random and alternating copolymers, terpolymers, and higher “x”mers,further including their derivatives, combinations, and blends thereof.Furthermore, unless otherwise specifically limited, the term “polymer”shall include all possible isomeric configurations of the monomers,including, but are not limited to isotactic, syndiotactic and randomconfigurations, and combinations thereof. Furthermore, unless otherwisespecifically limited, the term “polymer” shall include all possiblegeometrical configurations of the molecule.

As used herein, the term “solid” refers to a composition or material ina solid state. Solids can include powders, prills, beads or flakes.Powders can be prepared by grinding a larger solid composition, dryingout a paste, or other methods of preparing a solid powder, includingthose described herein. Preferably, a powder needs to be flowable.Preferably, a solid powder has non-cohesive powder flow properties asdetermined using a Brookfield powder flow tester. In preferredembodiments, a solid powder has a flow function (ff) of less than about0.4, more preferably less than about 0.35, most preferably between about0.15 and about 0.35.

As used herein, the term “ware” refers to items such as eating andcooking utensils, dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware. Ware also refers to items made ofplastic. Types of plastics that can be cleaned with the compositionsaccording to the invention include but are not limited to, those thatinclude polypropylene polymers (PP), polycarbonate polymers (PC),melamine formaldehyde resins or melamine resin (melamine),acrylonitrile-butadiene-styrene polymers (ABS), and polysulfonepolymers. Other exemplary plastics that can be cleaned using thecompounds and compositions include polyethylene terephthalate (PET)polystyrene polyamide.

The terms “water soluble” and “water miscible” as used herein, meansthat the component (e.g., solid surfactant or metal alkyl ether sulfate)is soluble or dispersible in water at about 20° C. at a concentrationgreater than about 50 g/L, preferably at about 55 g/L or greater, morepreferably at 60 g/L or greater, and most preferably at about 100 g/L orgreater.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods, systems, apparatuses, and compositions may comprise,consist essentially of, or consist of the components and ingredientsrecited as well as other components and ingredients described herein. Asused herein, “consisting essentially of” means that the methods,systems, apparatuses and compositions may include additional steps,components or ingredients, but only if the additional steps, componentsor ingredients do not materially alter the basic and novelcharacteristics of the claimed methods, systems, apparatuses, andcompositions.

Solidified Surfactant Blend:

The composition includes a solidified surfactant blend. The solidifiedsurfactant blend may be present in any amount, including and up to 100weight percent of the composition. In various embodiments, thesolidified surfactant blend is present in an amount of from 1 to 90weight percent based on a total weight of the composition, e.g. ±5 wt %.

In various embodiments, the solidified surfactant blend is present in anamount of from 5 to 95, 1 to 75, 10 to 85, 15 to 80, 20 to 75, 25 to 70,30 to 65, 35 to 60, 40 to 55, or 45 to 50, weight percent based on atotal weight of a cleaning composition. In other embodiments, thesolidified surfactant blend is present in an amount of 1, 2, 3, 4, or 5,weight percent based on a total weight of the composition.

The solidified surfactant blend includes (1) at least one metal alkylether sulfate and (2) a solid surfactant. In a preferred embodiment, thesolidified surfactant blend includes (1) at least one metal alkyl ethersulfate, (2) a solid surfactant, and (3) a polyethylene glycol. Invarious embodiments, the solidified surfactant blend can include two ormore (1) metal alkyl ether sulfates and/or two or more (2) solidsurfactants. In various embodiments, the solidified surfactant blend is,consists essentially of, or consists of (1) and (2), or (1), (2), and(3). The combination of (1) and (2) may be alternatively described as anamorphous component (i.e., (1)) disposed in a crystalline matrix (i.e.,(2)). In various embodiments, the composition is free of an alkylpolyglucoside (APG). In another embodiment, the composition is free ofan amide, which may be any amide known in the art such as any used in aliquid or solid cleaning composition.

Typically, (1) and (2) are present in a weight ratio of from 20:80 to70:30 based on a total weight of the solidified surfactant blend. Invarious embodiments, (1) is present such that the first value of theweight ratio is from 20 to 70, 25 to 65, 30 to 60, 35 to 55, 40 to 50,or 45 to 55. In other embodiments, (2) is present such that the secondvalue of the weight ratio is from 30 to 80, 25 to 75, 40 to 70, 45 to65, 50 to 60, or 55 to 60. In further embodiments, the weight ratio is50:50 or 30:70±1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In various non-limitingembodiments, all values and ranges of values including and between thosedescribed above are hereby expressly contemplated for use herein.

Metal Alkyl Ether Sulfate:

The (1) at least one metal alkyl ether sulfate has the formula:

wherein the first metal is sodium, potassium, magnesium, or calcium, ais 1 or 2, AO is ethylene oxide, propylene oxide, or combinationsthereof, x is 0.1 to 3, and y is 11 to 13. In various embodiments, thefirst metal is sodium. In other embodiments, the first metal ismagnesium. In still further embodiments, the first metal is potassium orcalcium. If the first metal is sodium or magnesium, a is 1. If the firstmetal is potassium or calcium, a is 2. In one embodiment, AO is ethyleneoxide. In another embodiment, AO is propylene oxide. In a furtherembodiment, AO is a combination of ethylene oxide and propylene oxide.It is also contemplated that AO (and the solidified surfactant blendand/or composition as a whole) may be free of propylene oxide, butyleneoxide, and/or any other oxides that are not ethylene oxide, and/or freeof reaction products thereof. In further embodiments, x represents thedegree of alkoxylation and is from 0.1 to 1, 0.2 to 0.9, 0.3 to 0.8, 0.4to 0.7, 0.5 to 0.6, 1 to 3, 1 to 2, 2 to 3, 1.5 to 2.5, 2 to 2.5, or 1.5to 3. In other embodiments, y represents a length of a carbon chain ofthe components and may be 11, 12, or 13. The (CH₂) moiety may be linearor branched. In various non-limiting embodiments, all values and rangesof values including and between those described above are herebyexpressly contemplated for use herein.

Solid Surfactant:

The solid surfactant may be any known in the art and may be crystallineor non-crystalline, and may be anionic, non-ionic, cationic, etc. Forexample, the solid surfactant may be chosen from Na LAS (sodium linearalkylbenzenesulfonate), sodium lauryl sulfoacetate, Sodium Alpha Olefinsulfonate (C14-16 AOS), disodium lauryl sulfosuccinate, sodium xylenesulfonate, sodium cumenesulfonate, and combinations thereof. In otherembodiments, the solid surfactant is chosen from alcohol ethoxylates,EO-PO block copolymers, amides (lauryl diethanolamide, cocamide DEA,cocoamide MEA, cocamide mono isopropanolamine PEG 6 lauramide, andcombinations thereof. All combinations of the aforementioned solidsurfactants are also expressly contemplated in various non-limitingembodiments.

Polyethylene Glycol

In a preferred embodiment, the solidified surfactant blend can comprisepolyethylene glycol (PEG), a polyethylene glycol derivative, orcombinations thereof. Preferably the PEG or PEG derivative has a weightaverage molecular weight of between about 1000 and 10,000, morepreferably from about 1400 to about 10,000 g/mol, Preferred PEGs includePEG 1450, PEG 3350, PEG 4000, PEG 4600, and PEG 8000. Preferably the PEGis in an amount of between about 1 wt. % and about 20 wt. %, morepreferably between about 5 wt. % and about 15 wt. % of the solidifiedsurfactant blend.

Metal Alkyl Sulfate:

The solid surfactant may be further defined as at least one (4) metalalkyl sulfate. The (4) at least one metal alkyl sulfate typically hasthe formula:

wherein the second metal is sodium, potassium, magnesium, or calcium,wherein b is 1 or 2, and wherein z is 11 to 13. In various embodiments,the second metal is sodium. In other embodiments, the second metal ismagnesium. In still further embodiments, the second metal is potassiumor calcium. If the second metal is sodium or magnesium, b is 1. If thesecond metal is potassium or calcium, b is 2. In further embodiments, zrepresents a length of a carbon chain of the components and may be 11,12, or 13. The (CH₂) moiety may be linear or branched. In variousnon-limiting embodiments, all values and ranges of values including andbetween those described above are hereby expressly contemplated for useherein.

Additional Surfactants:

As first introduced above, the solidified surfactant blend may furtherinclude, consist essentially of, or consist of, (5) a second metal alkylether sulfate component and/or (6) a second metal alkyl sulfate. These(5)/(6) second metal alkyl (ether) sulfates may be included in additionto (1), (2), and (3) above, in various embodiments.

The (5) second metal alkyl ether sulfate typically has the formula:

wherein the third metal is sodium, potassium, magnesium, or calcium, cis 1 or 2, AO is ethylene oxide, propylene oxide, or combinationsthereof, m is 0.1 to 3, and n is 11 to 13. In various embodiments, thethird metal is sodium. In other embodiments, the third metal ismagnesium. In still further embodiments, the third metal is potassium orcalcium. If the third metal is sodium or magnesium, c is 1. If the thirdmetal is potassium or calcium, c is 2. In one embodiment, AO is ethyleneoxide. In another embodiment, AO is propylene oxide. In a furtherembodiment, AO is a combination of ethylene oxide and propylene oxide.It is also contemplated that AO (and the solidified surfactant blendand/or composition as a whole) may be free of propylene oxide, butyleneoxide, and/or any other oxides that are not ethylene oxide, and/or freeof reaction products thereof. In further embodiments, m represents thedegree of alkoxylation and is from 0.1 to 1, 0.2 to 0.9, 0.3 to 0.8, 0.4to 0.7, 0.5 to 0.6, 1 to 3, 1 to 2, 2 to 3, 1.5 to 2.5, 2 to 2.5, or 1.5to 3. In other embodiments, n represents a length of a carbon chain ofthe components and may be 11, 12, or 13. The (CH₂) moiety may be linearor branched. In various non-limiting embodiments, all values and rangesof values including and between those described above are herebyexpressly contemplated for use herein.

In further embodiments, the (6) second metal alkyl sulfate typically hasthe formula:

wherein the fourth metal is sodium, potassium, magnesium, or calcium,wherein d is 1 or 2, and wherein t is 11 to 13. In various embodiments,the fourth metal is sodium. In other embodiments, the fourth metal ismagnesium. In still further embodiments, the fourth metal is potassiumor calcium. If the fourth metal is sodium or magnesium, d is 1. If thefourth metal is potassium or calcium, d is 2. In further embodiments, trepresents a length of a carbon chain of the components and may be 11,12, or 13. The (CH₂) moiety may be linear or branched. In variousnon-limiting embodiments, all values and ranges of values including andbetween those described above are hereby expressly contemplated for useherein.

In various embodiments, 85 to 100 weight percent of the solidifiedsurfactant blend is a combination of the (1) metal alkyl ether sulfateand the (2) solid surfactant, such as the (4) metal alkyl sulfatewherein each of y and z is 11. Moreover, 5 to 15 weight percent of thesolidified surfactant blend may be a combination of the (4) second metalalkyl ether sulfate and the (5) second metal alkyl sulfate wherein eachof n and t is 13. In other embodiments 90±1 weight percent of thesolidified surfactant blend is a combination of the (1) metal alkylether sulfate and the (2) (or (5)) wherein each of y and z is 11. Inaddition, 10±1 weight percent of the solidified surfactant blend may bea combination of the (4) second metal alkyl ether sulfate and the (5)second metal alkyl sulfate wherein each of n and t is 13. In still otherembodiments, 70 to 100 weight percent of the solidified surfactant blendis a combination of the (1) metal alkyl ether sulfate and the (4) metalalkyl sulfate wherein each of y and z is 11. Moreover, 25 to 35 weightpercent of the solidified surfactant blend may be a combination of the(5) second metal alkyl ether sulfate and the (6) second metal alkylsulfate wherein each of n and t is 13. In other embodiments, 70±1 weightpercent of the solidified surfactant blend is a combination of the (1)metal alkyl ether sulfate and the (4) metal alkyl sulfate wherein eachof y and z is 11. Furthermore, 30±1 weight percent of the solidifiedsurfactant blend may be a combination of the (5) second metal alkylether sulfate and the (6) second metal alkyl sulfate wherein each of nand t is 13. In various non-limiting embodiments, all values and rangesof values including and between those described above are herebyexpressly contemplated for use herein.

In still other embodiments, the solid cleaning composition includes lessthan 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent of, or is free of, oneor more of metal alkyl ether sulfates wherein y is 10 or less and/orwherein y is 14 or greater; metal alkyl sulfates wherein z is 10 or lessand/or wherein z is 14 or greater; second metal alkyl ether sulfateswherein n is 10 or less and/or wherein n is 14 or greater; and/or secondmetal alkyl sulfates wherein t is 10 or less and/or wherein t is 14 orgreater, or combinations thereof. Alternatively, the solid cleaningcomposition may include less than 5, 4, 3, 2, 1, 0.5, or 0.1, weightpercent of, or be free of, one or more of metal alkyl ether sulfateswherein AO is propylene oxide; and/or second metal alkyl ether sulfateswherein AO is propylene oxide, or any one or more of the solidsurfactants described above, or combinations thereof. In variousnon-limiting embodiments, all values and ranges of values including andbetween those described above are hereby expressly contemplated for useherein.

In additional embodiments, ((1) and optionally (5)) and ((4) andoptionally (6)) are present in a weight ratio of from 70:30 to 50:50 of(1+4):(3+5), or in any one or more of the aforementioned weight ratiosabove. In other embodiments, ((1) and optionally (5)) and ((4) andoptionally (6)) are present in a weight ratio of 70:30±5 of (1+4):(3+5),respectively, or in any one or more of the aforementioned weight ratiosabove.

Alkalinity Source for Solidified Surfactant Blend

The solidified surfactant blend can comprise one or more alkalinitysources. It has been found that the alkalinity source can providestability to the solidified surfactant blend, particularly at hightemperatures.

Alkalinity sources can include, but are not limited to carbonate-basedalkalinity sources, including, for example, carbonate salts such asalkali metal carbonates and bicarbonate; caustic-based alkalinitysources, including, for example, alkali metal hydroxides; other suitablealkalinity sources may include metal silicate, metal borate, and organicalkalinity sources. Exemplary alkali metal carbonates that can be usedinclude, but are not limited to, sodium carbonate, potassium carbonate,bicarbonate, sesquicarbonate, and mixtures thereof. Exemplary alkalimetal hydroxides that can be used include, but are not limited tosodium, lithium, or potassium hydroxide. Exemplary metal silicates thatcan be used include, but are not limited to, sodium or potassiumsilicate or metasilicate. Exemplary metal borates include, but are notlimited to, sodium or potassium borate.

Organic alkalinity sources are often strong nitrogen bases including,for example, ammonia (ammonium hydroxide), amines, alkanolamines, andamino alcohols. Typical examples of amines include primary, secondary ortertiary amines and diamines carrying at least one nitrogen linkedhydrocarbon group, which represents a saturated or unsaturated linear orbranched alkyl group having at least 10 carbon atoms and preferably16-24 carbon atoms, or an aryl, aralkyl, or alkaryl group containing upto 24 carbon atoms, and wherein the optional other nitrogen linkedgroups are formed by optionally substituted alkyl groups, aryl group oraralkyl groups or polyalkoxy groups. Typical examples of alkanolaminesinclude monoethanolamine, monopropanolamine, diethanolamine,dipropanolamine, triethanolamine, tripropanolamine and the like. Typicalexamples of amino alcohols include 2-amino-2-methyl-1-propanol,2-amino-1-butanol, 2-amino-2-methyl-1,3-propanediol,2-amino-2-ethyl-1,3-propanediol, hydroxymethyl aminomethane, and thelike.

When including an alkalinity source in the solidified surfactant blend,the alkalinity source is preferably added in an amount between about 0.1wt. % and 15 wt. %, more preferably between about 1 wt. % and about 12wt. %, most preferably between about 5 wt. % and about 10 wt. % of thesolidified surfactant blend.

Solid Cleaning Compositions

The solidified surfactant blend can be included in solid cleaningcompositions. Those cleaning compositions can include, but are notlimited to, detergent compositions, including, for example manualwarewash compositions, laundry compositions, and hard surface cleaningcompositions. Exemplary embodiments of those compositions are providedin Tables 1-3 below. In each of Tables 1-3, the surfactant componentcomprises the solidified surfactant blend. In some embodiments, the onlysurfactant added to the cleaning composition is the solidifiedsurfactant blend. In some embodiments, the surfactant is a combinationof the solidified surfactant blend and a co-surfactant. The compositionsrepresented in Tables 1-3 are exemplary and not limiting, for example,other cleaning compositions can be prepared with the solidifiedsurfactant blends described herein, and the cleaning compositionsreflected below are offered as examples of preferred formulations.

TABLE 1 Exemplary Manual Warewash Composition First Second ThirdExemplary Exemplary Exemplary Ingredient Range (wt. %) Range (wt. %)Range (wt. %) Alkalinity Source   0-10   0-5    1-10 Surfactant   30-95 40-90   40-90 Builders/Stabilizing  0.1-40 0.1-30  0.1-40 Agents Water0.01-20 0.1-10 0.01-10

TABLE 2 Exemplary Laundry Composition First Second Third ExemplaryExemplary Exemplary Ingredient Range (wt. %) Range (wt. %) Range (wt. %)Alkalinity Source   30-90  40-80 50-70 Surfactant 0.01-40 0.1-35  1-30Builders/Stabilizing   1-50   2-40  5-30 Agents Water   0-60 0.1-55 1-50

TABLE 3 Exemplary Hard Surface Cleaning Composition First FourthExemplary Second Third Exemplary Range Exemplary Exemplary RangeIngredient (wt. %) Range (wt. %) Range (wt. %) (wt. %) Surfactant   1-20  1-10   30-95   30-95 Builders/ 0.01-30 0.1-40  0.1-40  0.1-40Stabilizing Agents Alkalinity   30-90  40-90   20-50   0-10 Source Water0.01-20 0.1-10 0.01-10 0.01-10

Additive Components

In addition to the solidified surfactant blend, the composition may alsoinclude an additive component. Additive components can be added toprovide desired properties and functionalities to the compositions. Someparticular examples of additive components are discussed in more detailbelow, although the particular materials discussed are given by way ofexample only, and that a broad variety of other additive components maybe used. Examples of such additive components includechelating/sequestering agents; bleaching agents or activators;sanitizers/anti-microbial agents; activators; builder or fillers;anti-redeposition agents; optical brighteners; dyes; odorants orperfumes; preservatives; stabilizers; processing aids; corrosioninhibitors; fillers; solidifiers; hardening agent; solubility modifiers;pH adjusting agents; humectants; hydrotropes; color transfer inhibitors;foam inhibitors; complexing agents; enzymes; graying inhibitors;inorganic extenders; formulation auxiliaries; solubility improvers;opacifiers; electrolytes; soaps; detergents; soil release polymers;solvents; salts; water, or a broad variety of other additive components,depending upon the desired characteristics and/or functionality of thecomposition. In the context of some embodiments disclosed herein, theadditive components are optionally included within the solid cleaningcompositions for their functional properties. Some more particularexamples of additive components are discussed in more detail below, butit should be understood by those of skill in the art and others that theparticular materials discussed are given by way of example only, andthat a broad variety of other additive components may be used.

Some of the additional ingredients described below can be included inthe solid cleaning compositions comprised of a solidified surfactantblend. Preferred additional ingredients that can be incorporated intothe cleaning compositions include, but are not limited to, aco-surfactant, dye, fragrance (odorant) coco monoethanolamide, acombination of lauryl/myristyl glucoside (and) sodium sulfate (and)sodium silicate (and) sodium coco sulfate, MgSO₄, sodium acetate,cocamidopropylamineoxide, cocamidopropyl betaine, lauryliminodipropionate mono sodium salt, lauryldimethylamine oxide, MA/DIB/Halfester with alcohol ethoxylated, and combinations thereof.

The additive component may be present in any amount along with thesolidified surfactant blend. In various embodiments, the additivecomponent is present in an amount of from 10 to 99 weight percent, e.g.±5 wt %. In various embodiments, the additive component is present in anamount of from 10 to 95, 15 to 90, 20 to 85, 25 to 80, 30 to 75, 35 to70, 40 to 65, 45 to 60, or 50 to 55, weight percent. In variousnon-limiting embodiments, all values and ranges of values including andbetween those described above are hereby expressly contemplated for useherein.

Acid Source

In some embodiments, a cleaning composition can include an acid source.Suitable acid sources, can include, organic and/or inorganic acids.Examples of suitable organic acids include carboxylic acids such as butnot limited to hydroxyacetic (glycolic) acid, citric acid, formic acid,acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,trichloroacetic acid, urea hydrochloride, and benzoic acid, amongothers. Organic dicarboxylic acids such as oxalic acid, malonic acid,gluconic acid, itaconic acid, succinic acid, glutaric acid, maleic acid,fumaric acid, adipic acid, and terephthalic acid among others are alsouseful in accordance with the invention. Any combination of theseorganic acids may also be used intermixed or with other organic acidswhich allow adequate formation of the compositions.

Inorganic acids useful in accordance with the invention include sulfuricacid, sulfamic acid, methylsulfamic acid, hydrochloric acid, hydrobromicacid, and nitric acid among others. These acids may also be used incombination with other inorganic acids or with those organic acidsmentioned above. In a preferred embodiment, the acid is an inorganicacid.

In some embodiments, the cleaning compositions provide a pH of at leastabout, preferably at least about 5.5, more preferably at least about 6,most preferably at least about 6.5. In some embodiments, thecompositions provide a pH between about 6 and about 14, more preferablybetween about 6.5 and about 13, still more preferably between about 6.5and about 12, most preferably between about 7 and about 11.5. In someembodiments, the acid source can be included as a pH modifier orneutralizer in a composition to achieve a desired pH.

Activators

The composition may also include a bleach activator present in an amountof from 0.1 to 15% by weight. The bleach activator may include, but isnot limited to, polyacylated sugars, e.g., pentaacetylglucose,acyloxybenzenesulfonic acids and alkali metal and alkaline earth metalsalts thereof, e.g., sodium p-isononanoyloxybenzenesulfonate and sodiump-benzoyloxybenzenesulfonate, N,N-diacetylated andN,N,N′,N′-tetraacylated amines, e.g.,N,N,N′,N′-tetraacetylmethylenediamine and -ethylenediamine (TAED),N,Ndiacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylatedhydantoins, such as 1,3-diacetyl-5,5-dimethylhydantoin,N-alkyl-N-sulfonylcarboxamides, e.g., N-methyl-N-mesylacetamide andN-methyl-N-mesylbenzamide, N-acylated cyclic hydrazides, acylatedtriazoles and urazoles, e.g., monoacetylmaleic acid hydrazide,O,N,N-trisubstituted hydroxylamines, e.g.,O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxylamineand O, N,N-triacetylhydroxylamine, N,N′-diacylsulfurylamides, e.g.,N,N′-dimethyl-N,N′-diacetylsulfurylamide andN,N′-diethyl-N,N′-dipropionylsulfurylamide, triacyl cyanurates, e.g.,triacetyl cyanurate and tribenzoyl cyanurate, carboxylic anhydrides,e.g., benzoic acid anhydride, m-chlorobenzoic anhydride and phthalicanhydride, 1,3-diacyl-4,5-diacyloxyimidazolines, e.g.,1,3-diacetyl-4,5-diacetoxyimidazoline, tetraacetylglycoluril,tetrapropionylglycoluril, diacylated 2,5-diketopiperazines, e.g.,1,4-diacetyl-2,5-diketopiperazine, acylation products of propylenediureaand 2,2-dimethylpropylenediurea, e.g., tetraacetylpropylenediurea,a-acyloxypolyacylmalonamides, e.g., a-acetoxy-N,N′-diacetylmalonamide,diacyldioxohexahydro-1,3,5-triazines, e.g.,1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine,benz(4H)-1,3-oxazin-4-ones with alkyl radicals, e.g., methyl, oraromatic radicals, and combinations thereof.

The bleach may also be combined with a bleach catalyst. The bleachcatalyst may include, but is not limited to, quaternized imines,sulfonimines, manganese complexes, and combinations thereof. The bleachcatalyst may be included in the composition in amounts up to 1.5% byweight.

In some embodiments, a cleaning composition can have improved theantimicrobial activity or bleaching activity by the addition of amaterial which, when the composition is placed in use, reacts with theactive oxygen to form an activated component. For example, in someembodiments, a peracid or a peracid salt is formed. For example, in someembodiments, tetraacetylethylene diamine can be included within thecomposition to react with the active oxygen and form a peracid or aperacid salt that acts as an antimicrobial agent. Other examples ofactive oxygen activators include transition metals and their compounds,compounds that contain a carboxylic, nitrile, or ester moiety, or othersuch compounds known in the art. In an embodiment, the activatorincludes tetraacetylethylene diamine; transition metal; compound thatincludes carboxylic, nitrile, amine, or ester moiety; or mixturesthereof.

In some embodiments, an activator component can include in the range ofup to about 75% by wt. of the cleaning composition, in some embodiments,in the range of about 0.01 to about 20% by wt., or in some embodiments,in the range of about 0.05 to 10% by wt. of the cleaning composition. Insome embodiments, an activator for an active oxygen compound combineswith the active oxygen to form an antimicrobial agent.

The activator can be coupled to solid cleaning compositions by any of avariety of methods for coupling one solid cleaning composition toanother. For example, the activator can be in the form of a solid thatis bound, affixed, glued or otherwise adhered to the solid cleaningcomposition. Alternatively, the solid activator can be formed around andencasing the solid cleaning composition. By way of further example, thesolid activator can be coupled to the solid cleaning composition by thecontainer or package for the composition, such as by a plastic or shrinkwrap or film.

Alkalinity Source for Cleaning Compositions

The cleaning compositions can include an effective amount of one or morealkalinity sources. An effective amount of one or more alkaline sourcesshould be considered as an amount that provides a composition having apH between about 7 and about 14. In a particular embodiment the cleaningcompositions can have a pH of between about 7.5 and about 13.5. During awash cycle the use solution can have a pH between about 6 and about 14.In particular embodiments, the use solution can have a pH between about6 and 14. If the cleaning composition includes an enzyme composition,the pH may be modulated to provide the optimal pH range for the enzymecompositions effectiveness. In a particular embodiment incorporating anenzyme composition in the cleaning composition, the optimal pH isbetween about 10 and about 11.

Examples of suitable alkaline sources of the cleaning compositioninclude, but are not limited to carbonate-based alkalinity sources,including, for example, carbonate salts such as alkali metal carbonates;caustic-based alkalinity sources, including, for example, alkali metalhydroxides; other suitable alkalinity sources may include metalsilicate, metal borate, and organic alkalinity sources. Exemplary alkalimetal carbonates that can be used include, but are not limited to,sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate, andmixtures thereof. Exemplary alkali metal hydroxides that can be usedinclude, but are not limited to sodium, lithium, or potassium hydroxide.Exemplary metal silicates that can be used include, but are not limitedto, sodium or potassium silicate or metasilicate. Exemplary metalborates include, but are not limited to, sodium or potassium borate.

Organic alkalinity sources are often strong nitrogen bases including,for example, ammonia (ammonium hydroxide), amines, alkanolamines, andamino alcohols. Typical examples of amines include primary, secondary ortertiary amines and diamines carrying at least one nitrogen linkedhydrocarbon group, which represents a saturated or unsaturated linear orbranched alkyl group having at least 10 carbon atoms and preferably16-24 carbon atoms, or an aryl, aralkyl, or alkaryl group containing upto 24 carbon atoms, and wherein the optional other nitrogen linkedgroups are formed by optionally substituted alkyl groups, aryl group oraralkyl groups or polyalkoxy groups. Typical examples of alkanolaminesinclude monoethanolamine, monopropanolamine, diethanolamine,dipropanolamine, triethanolamine, tripropanolamine and the like. Typicalexamples of amino alcohols include 2-amino-2-methyl-1-propanol,2-amino-1-butanol, 2-amino-2-methyl-1,3-propanediol,2-amino-2-ethyl-1,3-propanediol, hydroxymethyl aminomethane, and thelike.

In general, alkalinity sources are commonly available in either aqueousor powdered form. Preferably, the alkalinity source is in a solid form.The alkalinity can be added to the composition in any form known in theart, including as solid beads, granulated or particulate form, dissolvedin an aqueous solution, or a combination thereof.

In a preferred embodiments, the cleaning compositions include analkalinity source in an amount between about 0.01% and about 99% byweight. In some embodiments, the alkalinity source will be between about35% and about 95% by weight of the total weight of the cleaningcomposition. When diluted to a use solution, the compositions caninclude between about 5 ppm and about 25,000 ppm of an alkalinitysource.

Anti-Redeposition Agents

The cleaning compositions can optionally include an anti-redepositionagent capable of facilitating sustained suspension of soils in acleaning or rinse solution and preventing removed soils from beingredeposited onto the substrate being cleaned and/or rinsed. Someexamples of suitable anti-redeposition agents can include fatty acidamides, fluorocarbon surfactants, complex phosphate esters, styrenemaleic anhydride copolymers, and cellulosic derivatives such ashydroxyethyl cellulose, hydroxypropyl cellulose, and the like. Acleaning composition can include up to about 10 wt. %, and in someembodiments, in the range of about 1 to about 5 wt. %, of ananti-redeposition agent.

Bleaching Agents

The cleaning compositions can optionally include bleaching agent.Bleaching agent can be used for lightening or whitening a substrate, andcan include bleaching compounds capable of liberating an active halogenspecies, such as Cl₂, Br₂, —OCl⁻ and/or —OBr⁻, or the like, underconditions typically encountered during the cleansing process. Suitablebleaching agents for use can include, for example, chlorine-containingcompounds such as a chlorine, a hypochlorite, chloramines, of the like.Some examples of halogen-releasing compounds include the alkali metaldichloroisocyanurates, chlorinated trisodium phosphate, the alkali metalhypochlorites, monochloramine and dichloroamine, and the like.Encapsulated chlorine sources may also be used to enhance the stabilityof the chlorine source in the composition (see, for example, U.S. Pat.Nos. 4,618,914 and 4,830,773, the disclosures of which are incorporatedby reference herein). A bleaching agent may also include an agentcontaining or acting as a source of active oxygen. The active oxygencompound acts to provide a source of active oxygen, for example, mayrelease active oxygen in aqueous solutions. An active oxygen compoundcan be inorganic or organic, or can be a mixture thereof. Some examplesof active oxygen compound include peroxygen compounds, or peroxygencompound adducts. Some examples of active oxygen compounds or sourcesinclude hydrogen peroxide, perborates, sodium carbonate peroxyhydrate,phosphate peroxyhydrates, potassium permonosulfate, and sodium perboratemono and tetrahydrate, with and without activators such astetraacetylethylene diamine, and the like.

Preferred bleaches may include, but is not limited to, alkali metalperborates, alkali metal carbonate perhydrates, peracids, hypochlorites,and combinations thereof. Suitable examples of peracids include, but arenot limited to, peracetic acid, C₁-C₁₂ percarboxylic acids, C₈-C₁₆dipercarboxylic acids, imidopercaproic acids, aryldipercaproic acids,linear and branched octane-, nonane-, decane- or dodecane-monoperacids,decane- and dodecane-diperacid, mono- and di-perphthalic acids,isophthalic acids and terephthalic acids, phthalimidopercaproic acid,terephthaloyldipercaproic acid, polymeric peracids, salts thereof, andcombinations thereof.

A cleaning composition may include a minor but effective amount of ableaching agent, for example, in some embodiments, in the range ofbetween about 0.5 wt. % and about 30 wt. %.

Builders

The cleaning compositions can comprise a builder. Preferred buildersinclude organic builders. Additionally, the organic builder may includea polyaspartic acid or a co-condensate of aspartic acid with one or moreamino acids including, but not limited to, C₄-C₂₅ mono- or di-carboxylicacids and/or C₄-C₂₅ mono- or di-amines. In one embodiment, theco-condensate includes a polyaspartic acid modified with C₆-C₂₂ mono- ordicarboxylic acids or with C₆-C₂₂ mono- or di-amines in acids includingphosphorous.

Further, the organic builder may include a condensation product ofcitric acid and a hydroxycarboxylic acid or a polyhydroxy compound. Mosttypically, the condensation products of citric acid include carboxylgroups and have number average molecular weights of up to 10,000 g/mol.Still further, the organic builder may include ethylenediaminedisuccinicacid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylenephosphonates, polyglutamates, and combinations thereof. Also, anon-limiting example of a suitable phosphonic acid includeshydroxyethanediphosphonic acid.

Alternatively, the organic builder may be selected from the group ofolefins, ethers, esters, amines, oxidized starches, and combinationsthereof. Suitable olefins, ethers, esters, and amines include, but arenot limited to, monoethylenically unsaturated C₂-C₂₂ olefins, vinylalkyl ethers with C₁-C₈ alkyl groups, styrene, vinyl esters of C₁-C₈carboxylic acids, (meth)acrylamide and vinylpyrrolidone, (meth)acrylicesters of C₁-C₈ alcohols, (meth)acrylonitrile, (meth)acrylamides ofC₁-C₈ amines, N-vinylformamide and vinylimidazole. In one embodiment,the organic builder is present in the composition in an amount of from0.1 to 20% by weight.

Carboxylic Acid Graft Polymers

Suitable examples of graft polymers of carboxylic acids include a graftbase and an unsaturated carboxylic acid. The carboxylic acid mayinclude, but is not limited to, maleic acid, fumaric acid, itaconicacid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid,vinylacetic acid, and combinations thereof. Suitable graft basesincluded in the graft polymers of the carboxylic acids include degradedpolysaccharides such as acidically and/or enzymatically degradedstarches, inulins, cellulose, protein hydrolysates, reduced degradedpolysaccharides such as mannitol, sorbitol, aminosorbitol andN-alkylglucamine, alkylene oxide block copolymers such as ethyleneoxide/propylene oxide block copolymers, ethylene oxide/butylene oxideblock copolymers, ethylene oxide/propylene oxide/butylene oxide blockcopolymers, and alkoxylated mono- or polyhydric C₁-C₇ alcohols and/orC₁₅-C₂₂ alcohols that are different from the first and secondsurfactants. It is to be understood that if alkoxylated mono- orpolyhydric C₁-C₇ alcohols and/or C₁₅-C₂₂ alcohols are included in thecomposition, these alkoxylated alcohols are not equivalent to the firstand second surfactants and may only be included in addition to the firstand second surfactants. In one embodiment, 20 to 80 parts by weight ofthe carboxylic acid per 100 parts by weight of the graft base, may bepolymerized. In this embodiment, a mixture of maleic acid and acrylicacid in the weight ratio from 90:10 to 10:90 is typically polymerizedwith the graft base.

Chelating/Sequestering Agents

The cleaning compositions may also include effective amounts ofchelating/sequestering agents, also referred to as builders. Inaddition, the cleaning compositions may optionally include one or moreadditional builders as a functional ingredient. In general, a chelatingagent is a molecule capable of coordinating (i.e., binding) the metalions commonly found in water sources to prevent the metal ions frominterfering with the action of the other ingredients of a rinse aid orother cleaning composition. The chelating/sequestering agent may alsofunction as a water conditioning agent when included in an effectiveamount. In some embodiments, a cleaning composition can include in therange of up to about 35 wt. %, or in the range of about 1-30 wt. %, of achelating/sequestering agent.

Often, the cleaning composition is also phosphate-free and/orsulfate-free. In embodiments of the solid cleaning composition that arephosphate-free, the additional functional materials, including buildersexclude phosphorous-containing compounds such as condensed phosphatesand phosphonates.

Suitable additional builders include aminocarboxylates andpolycarboxylates. Some examples of aminocarboxylates useful aschelating/sequestering agents, include, N-hydroxyethyliminodiaceticacid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid(EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA) (inaddition to the HEDTA used in the binder), diethylenetriaminepentaaceticacid (DTPA), methylglycine diacetic acid (MGDA), glutamic acid diaceticacid (GLDA), and the like. Some examples of polymeric polycarboxylatessuitable for use as sequestering agents include those having a pendantcarboxylate (—CO₂) groups and include, for example, polyacrylic acid,maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid,acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide,hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamidecopolymers, hydrolyzed polyacrylonitrile, hydrolyzedpolymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrilecopolymers, and the like.

In embodiments of the solid cleaning composition which are notphosphate-free, added chelating/sequestering agents may include, forexample a condensed phosphate, a phosphonate, and the like. Someexamples of condensed phosphates include sodium and potassiumorthophosphate, sodium and potassium pyrophosphate, sodiumtripolyphosphate, sodium hexametaphosphate, and the like. A condensedphosphate may also assist, to a limited extent, in solidification of thecomposition by fixing the free water present in the composition as waterof hydration.

In embodiments of the solid cleaning composition which are notphosphate-free, the composition may include a phosphonate such as1-hydroxyethane-1,1-diphosphonic acid CH₃C(OH)[PO(OH)₂]₂;aminotri(methylenephosphonic acid) N[CH₂ PO(OH)₂]₃;aminotri(methylenephosphonate), sodium salt

2-hydroxyethyliminobis(methylenephosphonic acid) HOCH₂ CH₂ N[CH₂PO(OH)₂]₂; diethylenetriaminepenta(methylenephosphonic acid) (HO)₂ POCH₂N[CH₂ N[CH₂ PO(OH)₂]₂]₂; diethylenetriaminepenta(methylenephosphonate),sodium salt C₉ H_((28-x)) N₃ Na_(x)O₁₅P₅ (x=7);hexamethylenediamine(tetramethylenephosphonate), potassium salt C₁₀H_((28-x))N₂K_(x)O₁₂P₄ (x=6);bis(hexamethylene)triamine(pentamethylenephosphonic acid)(HO₂)POCH₂NRCH₂)₆N[CH₂ PO(OH)₂]₂]₂; and phosphorus acid H₃PO₃. In someembodiments, a phosphonate combination such as ATMP and DTPMP may beused. A neutralized or alkaline phosphonate, or a combination of thephosphonate with an alkali source prior to being added into the mixturesuch that there is little or no heat or gas generated by aneutralization reaction when the phosphonate is added can be used.

For a further discussion of chelating agents/sequestrants, seeKirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume5, pages 339-366 and volume 23, pages 319-320, the disclosure of whichis incorporated by reference herein.

Color Transfer Inhibitors

Suitable color transfer inhibitors include, but are not limited to,color transfer inhibitors, for example homopolymers and copolymers ofvinylpyrrolidone, of vinylimidazole, of vinyloxazolidone and of4-vinylpyridine N-oxide having number average molecular weights of from15,000 to 100,000 g/mol. In one embodiment, the composition includes thecolor transfer inhibitor present in an amount of from 0.05 to 5% byweight.

Dicarboxylic Acid Copolymer

Examples of suitable copolymers of dicarboxylic acids include, but arenot limited to, copolymers of maleic acid and acrylic acid in a weightratio of 100:90 to 95:5 and more typically of 30:70 to 90:10 with molarmasses from 100,000 to 150,000, and copolymers of maleic acid with C₂-C₈olefins in a molar ratio 40:60 to 80:20. A non-limiting example of asuitable terpolymer of the carboxylic acids includes a terpolymer ofmaleic acid, acrylic acid and a vinyl ester of a C₁-C₃ carboxylic acidin a weight ratio of 10 (maleic acid):90 (acrylic acid+vinyl ester): 95(maleic acid):10 (acrylic acid+vinyl ester), where the weight ratio ofacrylic acid to the vinyl ester can be from 30:70 to 70:30.

Dyes/Odorants

Various dyes, odorants including perfumes, and other aesthetic enhancingagents may also be included in the solid cleaning compositions. Dyes maybe included to alter the appearance of the composition, as for example,FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (Sigma Chemical), DirectBlue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7(American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF),Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine andChemical), Metanil Yellow (Keystone Analine and Chemical), Acid Blue 9(Hilton Davis), Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red(Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical),Acid Green 25 (Ciba-Geigy), and the like.

Fragrances or perfumes that may be included in the solid cleaningcompositions include, for example, terpenoids such as citronellol,aldehydes such as amyl cinnamaldehyde, a jasmine such as C1S-jasmine orjasmal, vanillin, and the like.

Enzymes and Enzyme Stabilizers

The cleaning compositions can optionally include an enzyme. Preferredenzymes include enzymes that provide desirable activity for removal ofprotein-based, carbohydrate-based, or triglyceride-based stains from asurface; for cleaning, destaining, and sanitizing presoaks, such aspresoaks for medical and dental instruments, devices, and equipment;presoaks for flatware, cooking ware, and table ware; or presoaks formeat cutting equipment; for machine warewashing; for laundry and textilecleaning and destaining; for carpet cleaning and destaining; forcleaning-in-place and destaining-in-place; for cleaning and destainingfood processing surfaces and equipment; for drain cleaning; presoaks forcleaning; and the like. Although not limiting to the present invention,enzymes suitable for the solid detergent compositions can act bydegrading or altering one or more types of soil residues encountered onan instrument or device thus removing the soil or making the soil moreremovable by a surfactant or other component of the cleaningcomposition. Both degradation and alteration of soil residues canimprove detergency by reducing the physicochemical forces that bind thesoil to the instrument or device being cleaned, i.e., the soil becomesmore water soluble. For example, one or more proteases can cleavecomplex, macromolecular protein structures present in soil residues intosimpler short chain molecules which are, of themselves, more readilydesorbed from surfaces, solubilized or otherwise more easily removed bydetersive solutions containing said proteases.

Suitable enzymes include a protease, an amylase, a lipase, a gluconase,a cellulase, a peroxidase, a pectinase, a mannanase, or a mixturethereof of any suitable origin, such as vegetable, animal, bacterial,fungal or yeast origin. Preferred selections are influenced by factorssuch as pH-activity and/or stability optima, thermostability, andstability to active detergents, builders and the like. In this respectbacterial or fungal enzymes are preferred, such as bacterial amylasesand proteases, and fungal cellulases. Preferably the enzyme is aprotease, a lipase, an amylase, or a combination thereof.

“Detersive enzyme”, as used herein, means an enzyme having a cleaning,destaining or otherwise beneficial effect as a component of a soliddetergent composition for instruments, devices, or equipment, such asmedical or dental instruments, devices, or equipment; or for laundry,textiles, warewashing, cleaning-in-place, drains, carpets, meat cuttingtools, hard surfaces, personal care, or the like.

Preferred detersive enzymes include a hydrolase such as a protease, anamylase, a lipase, or a combination thereof. Preferred enzymes in soliddetergent compositions for cleaning medical or dental devices orinstruments include a protease, an amylase, a cellulase, a lipase, or acombination thereof.

Preferred enzymes in solid detergent compositions for food processingsurfaces and equipment include a protease, a lipase, an amylase, agluconase, or a combination thereof.

Preferred enzymes in solid detergent compositions for laundry ortextiles include a protease, a cellulase, a lipase, a peroxidase, or acombination thereof.

Preferred enzymes in solid detergent compositions for carpets include aprotease, an amylase, or a combination thereof.

Preferred enzymes in solid detergent compositions for meat cutting toolsinclude a protease, a lipase, or a combination thereof.

Preferred enzymes in solid detergent compositions for hard surfacesinclude a protease, a lipase, an amylase, or a combination thereof.

Preferred enzymes in solid detergent compositions for drains include aprotease, a lipase, an amylase, or a combination thereof.

Preferred enzymes include those commercially available include, but arenot limited to, the following: proteases such as Lavergy Pro, Savinase®and Esperase®, lipases such as Lipex®, cellulases such as Celluzym, andcombinations thereof. Each of the Savinase®, Esperase®, Lipolase®, andCelluclean are commercially available from Novozymes of Franklinton,N.C.

Enzymes are normally incorporated into a solid detergent compositionaccording to the invention in an amount sufficient to yield effectivecleaning during a washing or presoaking procedure. An amount effectivefor cleaning refers to an amount that produces a clean, sanitary, and,preferably, corrosion free appearance to the material cleaned,particularly for medical or dental devices or instruments. An amounteffective for cleaning also can refer to an amount that produces acleaning, stain removal, soil removal, whitening, deodorizing, orfreshness improving effect on substrates such as medical or dentaldevices or instruments and the like. Such a cleaning effect can beachieved with amounts of enzyme as low as about 0.1 wt-% of the soliddetergent composition. In the cleaning compositions of the presentinvention, suitable cleaning can typically be achieved when an enzyme ispresent at about 0.5 to about 25 wt-%; preferably about 1 to about 15wt-%; preferably about 1 to about 10 wt-%; preferably about 1 to about 8wt-%. The higher enzyme levels are typically desirable in highlyconcentrated cleaning or presoak formulations. A presoak is preferablyformulated for use upon a dilution of about 1:500, or to a formulationconcentration of about 2000 to about 4000 ppm, which puts the useconcentration of the enzyme at about 20 to about 40 ppm.

Commercial enzymes, such as alkaline proteases, are obtainable in liquidor dried form, are sold as raw aqueous solutions or in assortedpurified, processed and compounded forms, and include about 2% to about80% by weight active enzyme generally in combination with stabilizers,buffers, cofactors, impurities and inert vehicles. The actual activeenzyme content depends upon the method of manufacture and is notcritical; assuming the solid detergent composition has the desiredenzymatic activity. The particular enzyme chosen for use in the processand products of this invention depends upon the conditions of finalutility, including the physical product form, use pH, use temperature,and soil types to be degraded or altered. The enzyme can be chosen toprovide optimum activity and stability for any given set of utilityconditions.

The cleaning compositions of the present invention can include at leasta protease for cleaning protein-containing soils. Further, enhancedprotease activity can occur in the presence of one or more additionalenzymes, such as amylase, cellulase, lipase, peroxidase, endoglucanaseenzymes and mixtures thereof, preferably lipase or amylase enzymes.

A valuable reference on enzymes is “Industrial Enzymes”, Scott, D., inKirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, (editorsGrayson, M. and EcKroth, D.) Vol. 9, pp. 173 224, John Wiley & Sons, NewYork, 1980. When using enzymes, the methods of cleaning may also includethe use of an enzyme stabilizing agent.

Fillers

The solid cleaning compositions can optionally include a minor buteffective amount of one or more of a filler. Some examples of suitablefillers may include sodium chloride, starch, sugars, C₁-C₁₀ alkyleneglycols such as propylene glycol, sulfates, PEG, urea, sodium acetate,magnesium sulfate, sodium acetate, magnesium sulfate, sodium carbonateand the like. In some embodiments, a filler can be included in an amountin the range of up to about 50 wt. %, and in some embodiments, in therange of about 1-15 wt. %.

Foam Inhibitors

Suitable foam inhibitors include, but are not limited to,organopolysiloxanes, silica, paraffins, waxes, microcrystalline waxes,and combinations thereof.

Functional Polydimethylsiloxones

The solid cleaning composition can also optionally include one or morefunctional polydimethylsiloxones. For example, in some embodiments, apolyalkylene oxide-modified polydimethylsiloxane, nonionic surfactant ora polybetaine-modified polysiloxane amphoteric surfactant can beemployed as an additive. Both, in some embodiments, are linearpolysiloxane copolymers to which polyethers or polybetaines have beengrafted through a hydrosilation reaction. Some examples of specificsiloxane surfactants are known as SILWET® surfactants available fromUnion Carbide or ABIL® polyether or polybetaine polysiloxane copolymersavailable from Goldschmidt Chemical Corp., and described in U.S. Pat.No. 4,654,161 which patent is incorporated herein by reference. In someembodiments, the particular siloxanes used can be described as having,e.g., low surface tension, high wetting ability and excellent lubricity.For example, these surfactants are said to be among the few capable ofwetting polytetrafluoroethylene surfaces. The siloxane surfactantemployed as an additive can be used alone or in combination with afluorochemical surfactant. In some embodiments, the fluorochemicalsurfactant employed as an additive optionally in combination with asilane, can be, for example, a nonionic fluorohydrocarbon, for example,fluorinated alkyl polyoxyethylene ethanols, fluorinated alkyl alkoxylateand fluorinated alkyl esters.

Further description of such functional polydimethylsiloxones and/orfluorochemical surfactants are described in U.S. Pat. Nos. 5,880,088;5,880,089; and 5,603,776, all of which patents are incorporated hereinby reference. We have found, for example, that the use of certainpolysiloxane copolymers in a mixture with hydrocarbon surfactantsprovides excellent rinse aids on plastic ware. We have also found thatthe combination of certain silicone polysiloxane copolymers andfluorocarbon surfactants with conventional hydrocarbon surfactants alsoprovide excellent rinse aids on plastic ware. This combination has beenfound to be better than the individual components except with certainpolyalkylene oxide-modified polydimethylsiloxanes and polybetainepolysiloxane copolymers, where the effectiveness is about equivalent.Therefore, some embodiments encompass the polysiloxane copolymers aloneand the combination with the fluorocarbon surfactant can involvepolyether polysiloxanes, the nonionic siloxane surfactants. Theamphoteric siloxane surfactants, the polybetaine polysiloxane copolymersmay be employed alone as the additive in cleaning compositions toprovide the same results.

In some embodiments, the composition may include functionalpolydimethylsiloxones in an amount in the range of up to about 10 wt. %.For example, some embodiments may include in the range of about 0.1 to10 wt. % of a polyalkylene oxide-modified polydimethylsiloxane or apolybetaine-modified polysiloxane, optionally in combination with about0.1 to 10 wt. % of a fluorinated hydrocarbon nonionic surfactant.

Graying Inhibitors

Suitable graying inhibitors include, but are not limited to, polyestersof polyethylene oxides with ethylene glycol and/or propylene glycol andaromatic dicarboxylic acids or aromatic and aliphatic dicarboxylicacids, polyesters of polyethylene oxides terminally capped at one endwith di- and/or polyhydric alcohols or dicarboxylic acids, polyethyleneimines, polyethylene imine ethoxylates, and combinations thereof.

Hardening/Solidification Agents/Solubility Modifiers

In some embodiments, one or more solidification agents may be includedin the cleaning composition. Examples of hardening agents include urea,an amide such stearic monoethanolamide or lauric diethanolamide or analkylamide, and the like; sulfate salts or sulfated surfactants, andaromatic sulfonates, and the like; a solid polyethylene glycol, or asolid EO/PO block copolymer, and the like; starches that have been madewater-soluble through an acid or alkaline treatment process; variousinorganics that impart solidifying properties to a heated compositionupon cooling, and the like. Such compounds may also vary the solubilityof the composition in an aqueous medium during use such that the activeingredients may be dispensed from the solid composition over an extendedperiod of time.

Suitable aromatic sulfonates include, but are not limited to, sodiumxylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate,potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylenesulfonate, sodium alkyl naphthalene sulfonate, and/or sodium butylnaphthalene. Preferred aromatic sulfonates include sodium xylenesulfonate and sodium cumene sulfonate

The amount of solidification agent included in a cleaning compositioncan be dictated by the desired effect. In general, an effective amountof solidification agent is considered an amount that acts with orwithout other materials to solidify the cleaning composition. Typically,for solid embodiments, the amount of solidification agent in a cleaningcomposition is in a range of about 10 to about 80% by weight of thecleaning composition, preferably in the range of about 20 to about 75%by weight more preferably in the range of about 20 to about 70% byweight of the cleaning composition. The solidification agent issubstantially free of sulfate. For example, the cleaning composition mayhave less than 1 wt. % sulfate, preferably less than 0.5 wt. %, morepreferably less than 0.1 wt. %. In a preferred embodiment the cleaningcomposition is free of sulfate.

In certain embodiments it can be desirable to have a secondarysolidification agent. In compositions containing secondarysolidification the composition may include a secondary solidificationagent in an amount in the range of up to about 50 wt. %. In someembodiments, secondary hardening agents are may be present in an amountin the range of about 5 to about 35 wt. %, often in the range of about10 to about 25 wt. %, and sometimes in the range of about 5 to about 15wt.-%.

In some embodiments, one or more additional hardening agents may beincluded in the solid cleaning composition if desired. Examples ofhardening agents include an amide such stearic monoethanolamide orlauric diethanolamide, or an alkylamide, and the like; a solidpolyethylene glycol, or a solid EO/PO block copolymer, and the like;starches that have been made water-soluble through an acid or alkalinetreatment process; various inorganics that impart solidifying propertiesto a heated composition upon cooling, and the like. Such compounds mayalso vary the solubility of the composition in an aqueous medium duringuse such that the ingredients may be dispensed from the solidcomposition over an extended period of time. The composition may includea secondary hardening agent in an amount in the range of up to about 30wt. %. In some embodiments, secondary hardening agents are may bepresent in an amount in the range of about 5 to about 25 wt. %, often inthe range of about 10 to about 25 wt. %, and sometimes in the range ofabout 5 to about 15 wt. %.

Humectant

The solid cleaning composition can also optionally include one or morehumectants. A humectant is a substance having an affinity for water. Thehumectant can be provided in an amount sufficient to aid in reducing thevisibility of a film on the substrate surface. The visibility of a filmon substrate surface is a particular concern when the rinse watercontains in excess of 200 ppm total dissolved solids. Accordingly, insome embodiments, the humectant is provided in an amount sufficient toreduce the visibility of a film on a substrate surface when the rinsewater contains in excess of 200 ppm total dissolved solids compared to arinse agent composition not containing the humectant. The terms “watersolids filming” or “filming” refer to the presence of a visible,continuous layer of matter on a substrate surface that gives theappearance that the substrate surface is not clean.

Some example humectants that can be used include those materials thatcontain greater than 5 wt. % water (based on dry humectant) equilibratedat 50% relative humidity and room temperature. Exemplary humectants thatcan be used include glycerin, propylene glycol, sorbitol, alkylpolyglycosides, polybetaine polysiloxanes, and mixtures thereof. In someembodiments, the rinse agent composition can include humectant in anamount in the range of up to about 75% based on the total composition,and in some embodiments, in the range of about 5 wt. % to about 75 wt. %based on the weight of the composition.

Hydratable Salt

The solid cleaning compositions according to the invention canoptionally comprise at least one hydratable salt. In an embodiment thehydratable salt is sodium carbonate (aka soda ash or ash) and/orpotassium carbonate (aka potash). In a preferred aspect, the hydratablesalt is sodium carbonate and excludes potassium carbonate. Thehydratable salt can be provided in the ranges from between approximately20% and approximately 90% by weight, preferably between approximately25% and approximately 90% by weight, and more preferably betweenapproximately 30% and approximately 70% by weight hydratable salt, suchas sodium carbonate. Those skilled in the art will appreciate othersuitable component concentration ranges for obtaining comparableproperties of the solidification matrix.

In other embodiments, the hydratable salt may be combined with othersolidification agents. For example, the hydratable salt may be used withadditional solidification agents that are inorganic in nature and mayalso act optionally as a source of alkalinity. In certain embodiments,the secondary solidification agent may include, but are not limited to:additional alkali metal hydroxides, anhydrous sodium carbonate,anhydrous sodium sulfate, anhydrous sodium acetate, and other knownhydratable compounds or combinations thereof. According to a preferredembodiment, the secondary hydratable salt comprises sodium metasilicateand/or anhydrous sodium metasilicate. The amount of secondarysolidifying agent necessary to achieve solidification depends uponseveral factors, including the exact solidifying agent employed, theamount of water in the composition, and the hydration capacity of theother cleaning composition components. In certain embodiments, thesecondary solidifying agent may also serve as an additional alkalinesource.

Polymer

The cleaning compositions can include a polymer or a polymer systemcomprised of at least one polycarboxylic acid polymer, copolymer, and/orterpolymer. Particularly suitable polycarboxylic acid polymers, include,but are not limited to, polymaleic acid homopolymers, polyacrylic acidcopolymers, and maleic anhydride/olefin copolymers.

Polymaleic acid (C₄H₂O₃)x or hydrolyzed polymaleic anhydride orcis-2-butenedioic acid homopolymer, has the structural formula:

where n and m are any integer and wherein maleic acid moieties andmaleic anhydride moieties may be arranged statistically or block-wise.Examples of polymaleic acid homopolymers, copolymers, and/or terpolymers(and salts thereof) which may be used for the invention are particularlypreferred are those with a molecular weight of about 1000 and about25,000, more preferably between about 1000 and about 5000. Commerciallyavailable polymaleic acid homopolymers include the Belclene 200 seriesof maleic acid homopolymers from BWA™ Water Additives, 979 LakesideParkway, Suite 925 Tucker, GA 30084, USA and Aquatreat AR-801 availablefrom AkzoNobel. The polymaleic acid homopolymers, copolymers, and/orterpolymers may be present in cleaning compositions from about 0.01 wt.% to about 30 wt. %.

The cleaning compositions can use polyacrylic acid polymers, copolymers,and/or terpolymers. Poly acrylic acids have the following structuralformula:

where n is any integer. Examples of suitable polyacrylic acid polymers,copolymers, and/or terpolymers, include but are not limited to, thepolymers, copolymers, and/or terpolymers of polyacrylic acids,(C₃H₄O₂)_(n) or 2-Propenoic acid, acrylic acid, polyacrylic acid,propenoic acid.

In an embodiment, particularly suitable acrylic acid polymers,copolymers, and/or terpolymers have a molecular weight between about 100and about 10,000, in a preferred embodiment between about 500 and about7000, in an even more preferred embodiment between about 1000 and about5000, and in a most preferred embodiment between about 1500 and about3500. Examples of polyacrylic acid polymers, copolymers, and/orterpolymers (or salts thereof) which may be used for the inventioninclude, but are not limited to, Acusol 448 and Acusol 425 from The DowChemical Company, Wilmington Del., USA. In particular embodiments it maybe desirable to have acrylic acid polymers (and salts thereof) withmolecular weights greater than about 10,000. Examples, include but arenot limited to, Acusol 929 (10,000 MW) and Acumer 1510 (60,000 MW) bothalso available from Dow Chemical, AQUATREAT AR-6 (100,000 MW) fromAkzoNobel Strawinskylaan 2555 1077 ZZ Amsterdam Postbus 75730 1070 ASAmsterdam. The polyacrylic acid polymer, copolymer, and/or terpolymermay be present in the compositions from about may be present in cleaningcompositions from about 0.01 wt. % to about 30 wt. %.

Maleic anhydride/olefin copolymers are copolymers of polymaleicanhydrides and olefins. Maleic anhydride (C₂H₂(CO)₂O has the followingstructure:

A part of the maleic anhydride can be replaced by maleimide,N-alkyl(C₁₋₄) maleimides, N-phenyl-maleimide, fumaric acid, itaconicacid, citraconic acid, aconitic acid, crotonic acid, cinnamic 10 acid,alkyl (C₁₋₁₈) esters of the foregoing acids, cycloalkyl(C₃₋₈) esters ofthe foregoing acids, sulfated castor oil, or the like.

At least 95 wt % of the maleic anhydride polymers, copolymers, orterpolymers have a number average molecular weight of in the rangebetween about 700 and about 20,000, preferably between about 1000 andabout 100,000.

A variety of linear and branched chain alpha-olefins can be used for thepurposes of this invention. Particularly useful alpha-olefins are dienescontaining 4 to 18 carbon atoms, such as butadiene, chloroprene,isoprene, and 2-methyl-1,5-hexadiene; 1-alkenes containing 4 to 8 carbonatoms, preferably C₄-10, such as isobutylene, 1-butene, 1-hexene,1-octene, and the like.

In an embodiment, particularly suitable maleic anhydride/olefincopolymers have a molecular weight between about 1000 and about 50,000,in a preferred embodiment between about 5000 and about 20,000, and in amost preferred embodiment between about 7500 and about 12,500. Examplesof maleic anhydride/olefin copolymers which may be used for theinvention include, but are not limited to, Acusol 460N from The DowChemical Company, Wilmington Del., USA. The maleic anhydride/olefincopolymer may be present in cleaning compositions from about 0.01 wt. %to about 30 wt. %.

Sanitizers/Anti-Microbial Agents

The cleaning compositions can optionally include a sanitizing agent.Sanitizing agents also known as antimicrobial agents are chemicalcompositions that can be used in a solid functional material to preventmicrobial contamination and deterioration of material systems, surfaces,etc. Generally, these materials fall in specific classes includingphenolics, halogen compounds, quaternary ammonium compounds, metalderivatives, amines, alkanol amines, nitro derivatives, analides,organosulfur and sulfur-nitrogen compounds and miscellaneous compounds.

It should also be understood that active oxygen compounds, such as thosediscussed above in the bleaching agents section, may also act asantimicrobial agents, and can even provide sanitizing activity. In fact,in some embodiments, the ability of the active oxygen compound to act asan antimicrobial agent reduces the need for additional antimicrobialagents within the composition. For example, percarbonate compositionshave been demonstrated to provide excellent antimicrobial action.Nonetheless, some embodiments incorporate additional antimicrobialagents.

The given antimicrobial agent, depending on chemical composition andconcentration, may simply limit further proliferation of numbers of themicrobe or may destroy all or a portion of the microbial population. Theterms “microbes” and “microorganisms” typically refer primarily tobacteria, virus, yeast, spores, and fungus microorganisms. In use, theantimicrobial agents are typically formed into a solid functionalmaterial that when diluted and dispensed, optionally, for example, usingan aqueous stream forms an aqueous disinfectant or sanitizer compositionthat can be contacted with a variety of surfaces resulting in preventionof growth or the killing of a portion of the microbial population. Athree-log reduction of the microbial population results in a sanitizercomposition. The antimicrobial agent can be encapsulated, for example,to improve its stability.

Some examples of common antimicrobial agents include phenolicantimicrobials such as pentachlorophenol, orthophenylphenol, achloro-p-benzylphenol, p-chloro-m-xylenol. Halogen containingantibacterial agents include sodium trichloroisocyanurate, sodiumdichloro isocyanate (anhydrous or dihydrate),iodine-poly(vinylpyrolidinone) complexes, bromine compounds such as2-bromo-2-nitropropane-1,3-diol, and quaternary antimicrobial agentssuch as benzalkonium chloride, didecyldimethyl ammonium chloride,choline diiodochloride, tetramethyl phosphonium tribromide. Otherantimicrobial compositions such ashexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates suchas sodium dimethyldithiocarbamate, and a variety of other materials areknown in the art for their antimicrobial properties.

In embodiments of the solid cleaning composition which arephosphate-free, and/or sulfate-free, and also include an anti-microbialagent, the anti-microbial is selected to meet those requirements.Embodiments of the solid cleaning composition which include only GRASingredients, may exclude or omit anti-microbial agents described in thissection.

In some embodiments, the cleaning composition comprises, anantimicrobial component in the range of up to about 10% by wt. of thecomposition, in some embodiments in the range of up to about 5 wt. %, orin some embodiments, in the range of about 0.01 to about 3 wt. %, or inthe range of 0.05 to 1% by wt. of the composition.

Soil Release Polymers

Suitable soil release polymers include, but are not limited to,amphiphilic graft polymers or copolymers of vinyl esters and/or acrylicesters onto polyalkylene oxides or modified celluloses, such asmethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose, andcombinations thereof. In one embodiment, the composition includes thesoil release polymer present in an amount of from 0.3 to 1.5% by weight.

Solvents

Various solvents can be incorporated into the solid cleaningcompositions. Preferred solvents include, but are not limited to,ethylene glycol, 2-butoxyethanol, butyldiglycol, alkyl glycol ethers,and isopropanol.

Additional Surfactants

The solidified surfactant blend and/or solid cleaning compositions caninclude optional co-surfactants. Preferably, a co-surfactant is in solidform. Further, the solidified surfactant blend and/or solid cleaningcompositions can be incorporated in cleaning compositions. Thosecleaning compositions can include, but are not limited to, detergentcompositions, warewash compositions, laundry compositions, rinse aids,and hard surface cleaning compositions. Surfactants that can be includedas a co-surfactant in the solidified surfactant blend and/or solidcleaning compositions, include, nonionic surfactants, semi polarnonionic surfactants, anionic surfactants, cationic surfactants,amphoteric surfactants, zwitterionic surfactants, and mixtures orcombinations of the same.

When including a co-surfactant in the solidified surfactant blend and/orsolid cleaning compositions, the co-surfactant is preferably present inamount of about 20 wt. % to about 90 wt. %, more preferably from about30 wt. % to about 90 wt. %, and more preferably from about 40 wt. % toabout 80 wt. %.

Nonionic Surfactants

Useful nonionic surfactants are generally characterized by the presenceof an organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants include:

(1) Block polyoxypropylene-polyoxyethylene polymeric compounds basedupon propylene glycol, ethylene glycol, glycerol, trimethylolpropane,and ethylenediamine as the initiator reactive hydrogen compound.Examples of polymeric compounds made from a sequential propoxylation andethoxylation of initiator are commercially available from BASF Corp. Oneclass of compounds are difunctional (two reactive hydrogens) compoundsformed by condensing ethylene oxide with a hydrophobic base formed bythe addition of propylene oxide to the two hydroxyl groups of propyleneglycol. This hydrophobic portion of the molecule weighs from about 1,000to about 4,000. Ethylene oxide is then added to sandwich this hydrophobebetween hydrophilic groups, controlled by length to constitute fromabout 10% by weight to about 80% by weight of the final molecule.Another class of compounds are tetra-flinctional block copolymersderived from the sequential addition of propylene oxide and ethyleneoxide to ethylenediamine. The molecular weight of the propylene oxidehydrotype ranges from about 500 to about 7,000; and, the hydrophile,ethylene oxide, is added to constitute from about 10% by weight to about80% by weight of the molecule.

(2) Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from about 8 to about 18 carbonatoms with from about 3 to about 50 moles of ethylene oxide. The alkylgroup can, for example, be represented by diisobutylene, di-amyl,polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactantscan be polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols. Examples of commercial compounds of this chemistry areavailable on the market under the trade names Igepal® manufactured byRhone-Poulenc and Triton® manufactured by Union Carbide.

(3) Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from about 6 to about 24carbon atoms with from about 3 to about 50 moles of ethylene oxide. Thealcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range. Examples of likecommercial surfactant are available under the trade names Lutensol™,Dehydol™ manufactured by BASF, Neodol™ manufactured by Shell ChemicalCo. and Alfonic™ manufactured by Vista Chemical Co.

(4) Condensation products of one mole of saturated or unsaturated,straight or branched chain carboxylic acid having from about 8 to about18 carbon atoms with from about 6 to about 50 moles of ethylene oxide.The acid moiety can consist of mixtures of acids in the above definedcarbon atoms range or it can consist of an acid having a specific numberof carbon atoms within the range. Examples of commercial compounds ofthis chemistry are available on the market under the trade namesDisponil manufactured by BASF and Lipopeg™ manufactured by LipoChemicals, Inc.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances.

Examples of nonionic low foaming surfactants include:

(5) Compounds from (1) which are modified, essentially reversed, byadding ethylene oxide to ethylene glycol to provide a hydrophile ofdesignated molecular weight; and, then adding propylene oxide to obtainhydrophobic blocks on the outside (ends) of the molecule. Thehydrophobic portion of the molecule weighs from about 1,000 to about3,100 with the central hydrophile including 10% by weight to about 80%by weight of the final molecule. These reverse Pluronics™ aremanufactured by BASF Corporation under the trade name Pluronic™ Rsurfactants. Likewise, the Tetronic™ R surfactants are produced by BASFCorporation by the sequential addition of ethylene oxide and propyleneoxide to ethylenediamine. The hydrophobic portion of the molecule weighsfrom about 2,100 to about 6,700 with the central hydrophile including10% by weight to 80% by weight of the final molecule.

(6) Compounds from groups (1), (2), (3) and (4) which are modified by“capping” or “end blocking” the terminal hydroxy group or groups (ofmulti-functional moieties) to reduce foaming by reaction with a smallhydrophobic molecule such as propylene oxide, butylene oxide, benzylchloride; and, short chain fatty acids, alcohols or alkyl halidescontaining from 1 to about 5 carbon atoms; and mixtures thereof. Alsoincluded are reactants such as thionyl chloride which convert terminalhydroxy groups to a chloride group. Such modifications to the terminalhydroxy group may lead to all-block, block-heteric, heteric-block orall-heteric nonionics.

Additional examples of effective low foaming nonionics include:

(7) The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issuedSep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkylene oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆O)_(n) (C₂H₄O)_(m)H wherein Y is the residue of organiccompound having from about 1 to 6 carbon atoms and one reactive hydrogenatom, n has an average value of at least about 6.4, as determined byhydroxyl number and m has a value such that the oxyethylene portionconstitutes about 10% to about 90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O_(n) (C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from about 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least about 2, n has a valuesuch that the molecular weight of the polyoxypropylene hydrophobic baseis at least about 900 and m has value such that the oxyethylene contentof the molecule is from about 10% to about 90% by weight. Compoundsfalling within the scope of the definition for Y include, for example,propylene glycol, glycerine, pentaerythritol, trimethylolpropane,ethylenediamine and the like. The oxypropylene chains optionally, butadvantageously, contain small amounts of ethylene oxide and theoxyethylene chains also optionally, but advantageously, contain smallamounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n) (C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from about 8 to 18 carbon atoms andcontaining x reactive hydrogen atoms in which x has a value of 1 or 2, nhas a value such that the molecular weight of the polyoxyethyleneportion is at least about 44 and m has a value such that theoxypropylene content of the molecule is from about 10% to about 90% byweight. In either case the oxypropylene chains may contain optionally,but advantageously, small amounts of ethylene oxide and the oxyethylenechains may contain also optionally, but advantageously, small amounts ofpropylene oxide.

(8) Polyhydroxy fatty acid amide surfactants suitable for use in thepresent compositions include those having the structural formulaR₂CON_(R1)Z in which: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl,2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R₂ is aC₅-C₃₁ hydrocarbyl, which can be straight-chain; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z can be derived froma reducing sugar in a reductive amination reaction; such as a glycitylmoiety.

(9) The alkyl ethoxylate condensation products of aliphatic alcoholswith from about 0 to about 25 moles of ethylene oxide are suitable foruse in the present compositions. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contains from 6 to 22 carbon atoms.

(10) The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylatedand propoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-C₁₈ ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

(11) Suitable nonionic alkylpolysaccharide surfactants, particularly foruse in the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside.) The intersaccharide bonds can be, e.g., between the oneposition of the additional saccharide units and the 2-, 3-, 4-, and/or6-positions on the preceding saccharide units.

(12) Fatty acid amide surfactants suitable for use the presentcompositions include those having the formula: R₆CON(R7)₂ in which R₆ isan alkyl group containing from 7 to 21 carbon atoms and each R₇ isindependently hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or —(C₂H₄O)xH,where x is in the range of from 1 to 3.

(13) A useful class of non-ionic surfactants include the class definedas alkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)_(S)N-(EO)_(t)H, R²⁰—(PO)_(S)N-(EO)_(t)H(EO)_(t)H, andR²⁰—N(EO)_(t)H; in which R²⁰ is an alkyl, alkenyl or other aliphaticgroup, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20,preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably2-5. Other variations on the scope of these compounds may be representedby the alternative formula: R²⁰—(PO)_(V)—N[(EO)_(w)H][(EO)_(z)H] inwhich R²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4(preferably 2)), and w and z are independently 1-10, preferably 2-5.These compounds are represented commercially by a line of products soldby Huntsman Chemicals as nonionic surfactants. A preferred chemical ofthis class includes Surfonic™ PEA 25 Amine Alkoxylate. Preferrednonionic surfactants for the compositions include alcohol alkoxylates,EO/PO block copolymers, alkylphenol alkoxylates, and the like.

Semi Polar Nonionic Surfactants

The semi-polar type of nonionic surface active agents are another classof nonionic surfactant useful in compositions. Generally, semi-polarnonionics are high foamers and foam stabilizers, which can limit theirapplication in CIP systems. However, within compositional embodiments ofthis invention designed for high foam cleaning methodology, semi-polarnonionics would have immediate utility. The semi-polar nonionicsurfactants include the amine oxides, phosphine oxides, sulfoxides andtheir alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkalineor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are dodecyldimethylamine oxide, tridecyldimethylamine oxide,etradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 toabout 24 carbon atoms in chain length; and, R² and R³ are each alkylmoieties separately selected from alkyl or hydroxyalkyl groupscontaining 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphoneoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyldecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include the watersoluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbonatoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxylsubstituents; and R² is an alkyl moiety consisting of alkyl andhydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants for the compositions include dimethylamine oxides, such as lauryl dimethyl amine oxide, myristyl dimethylamine oxide, cetyl dimethyl amine oxide, combinations thereof, and thelike. Useful water soluble amine oxide surfactants are selected from theoctyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(loweralkyl) amine oxides, specific examples of which are octyldimethylamineoxide, nonyldimethylamine oxide, decyldimethylamine oxide,undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Nonionic surfactants suitable for use with the compositions includealkoxylated surfactants. Suitable alkoxylated surfactants include EO/POcopolymers, capped EO/PO copolymers, alcohol alkoxylates, capped alcoholalkoxylates, mixtures thereof, or the like. Suitable alkoxylatedsurfactants for use as solvents include EO/PO block copolymers, such asthe Pluronic and reverse Pluronic surfactants; alcohol alkoxylates, suchas Dehypon LS-54 (R-(EO)₅(PO)₄) and Dehypon LS-36 (R-(EO)₃(PO)₆); andcapped alcohol alkoxylates, such as Plurafac LF221 and Tegoten EC11;mixtures thereof, or the like.

Anionic Surfactants

Also useful in the compositions are surface active substances which arecategorized as anionics because the charge on the hydrophobe isnegative; or surfactants in which the hydrophobic section of themolecule carries no charge unless the pH is elevated to neutrality orabove (e.g. carboxylic acids). Carboxylate, sulfonate, sulfate andphosphate are the polar (hydrophilic) solubilizing groups found inanionic surfactants. Of the cations (counter ions) associated with thesepolar groups, sodium, lithium and potassium impart water solubility;ammonium and substituted ammonium ions provide both water and oilsolubility; and, calcium, barium, and magnesium promote oil solubility.As those skilled in the art understand, anionics are excellent detersivesurfactants and are therefore favored additions to heavy duty detergentcompositions.

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleicacid, and the like. Such carboxylates include alkyl ethoxy carboxylates,alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylatesurfactants and soaps (e.g. alkyl carboxyls). Secondary carboxylatesuseful in the present compositions include those which contain acarboxyl unit connected to a secondary carbon. The secondary carbon canbe in a ring structure, e.g. as in p-octyl benzoic acid, or as inalkyl-substituted cyclohexyl carboxylates. The secondary carboxylatesurfactants typically contain no ether linkages, no ester linkages andno hydroxyl groups. Further, they typically lack nitrogen atoms in thehead-group (amphiphilic portion). Suitable secondary soap surfactantstypically contain 11-13 total carbon atoms, although more carbons atoms(e.g., up to 16) can be present. Suitable carboxylates also includeacylamino acids (and salts), such as acylgluamates, acyl peptides,sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyl tauratesand fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:

R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X  (3)

in which R is a C₈ to C₂₂ alkyl group or

in which R¹ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₅-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R¹ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R¹ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form. Commerciallyavailable carboxylates include, Neodox 23-4, a C₁₂₋₁₃ alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP-110, a C₉ alkylarylpolyethoxy (10) carboxylic acid (Witco Chemical). Carboxylates are alsoavailable from Clariant, e.g. the product Sandopan® DTC, a C₁₃ alkylpolyethoxy (7) carboxylic acid.

Cationic Surfactants

Surface active substances are classified as cationic if the charge onthe hydrotrope portion of the molecule is positive. Surfactants in whichthe hydrotrope carries no charge unless the pH is lowered close toneutrality or lower, but which are then cationic (e.g. alkyl amines),are also included in this group. In theory, cationic surfactants may besynthesized from any combination of elements containing an “onium”structure RnX+Y— and could include compounds other than nitrogen(ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium). Inpractice, the cationic surfactant field is dominated by nitrogencontaining compounds, probably because synthetic routes to nitrogenouscationics are simple and straightforward and give high yields ofproduct, which can make them less expensive.

Cationic surfactants preferably include, more preferably refer to,compounds containing at least one long carbon chain hydrophobic groupand at least one positively charged nitrogen. The long carbon chaingroup may be attached directly to the nitrogen atom by simplesubstitution; or more preferably indirectly by a bridging functionalgroup or groups in so-called interrupted alkylamines and amido amines.Such functional groups can make the molecule more hydrophilic and/ormore water dispersible, more easily water solubilized by co-surfactantmixtures, and/or water soluble. For increased water solubility,additional primary, secondary or tertiary amino groups can be introducedor the amino nitrogen can be quaternized with low molecular weight alkylgroups. Further, the nitrogen can be a part of branched or straightchain moiety of varying degrees of unsaturation or of a saturated orunsaturated heterocyclic ring. In addition, cationic surfactants maycontain complex linkages having more than one cationic nitrogen atom.

The surfactant compounds classified as amine oxides, amphoterics andzwitterions are themselves typically cationic in near neutral to acidicpH solutions and can overlap surfactant classifications.Polyoxyethylated cationic surfactants generally behave like nonionicsurfactants in alkaline solution and like cationic surfactants in acidicsolution.

The simplest cationic amines, amine salts and quaternary ammoniumcompounds can be schematically drawn thus:

in which, R represents an alkyl chain, R′, R″, and R′″ may be eitheralkyl chains or aryl groups or hydrogen and X represents an anion. Theamine salts and quaternary ammonium compounds are preferred forpractical use in this invention due to their high degree of watersolubility.

The majority of large volume commercial cationic surfactants can besubdivided into four major classes and additional sub-groups known tothose or skill in the art and described in “Surfactant Encyclopedia”,Cosmetics & Toiletries, Vol. 104 (2) 86-96 (1989). The first classincludes alkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourthclass includes quaternaries, such as alkylbenzyldimethylammonium salts,alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammoniumsalts, and the like. Cationic surfactants are known to have a variety ofproperties that can be beneficial in the present compositions. Thesedesirable properties can include detergency in compositions of or belowneutral pH, antimicrobial efficacy, thickening or gelling in cooperationwith other agents, and the like.

Cationic surfactants useful in the compositions include those having theformula R¹ _(m)R² _(x)Y_(L)Z wherein each R¹ is an organic groupcontaining a straight or branched alkyl or alkenyl group optionallysubstituted with up to three phenyl or hydroxy groups and optionallyinterrupted by up to four of the following structures:

or an isomer or mixture of these structures, and which contains fromabout 8 to 22 carbon atoms. The R¹ groups can additionally contain up to12 ethoxy groups. m is a number from 1 to 3. Preferably, no more thanone R¹ group in a molecule has 16 or more carbon atoms when m is 2 ormore than 12 carbon atoms when m is 3. Each R² is an alkyl orhydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl groupwith no more than one R² in a molecule being benzyl, and x is a numberfrom 0 to 11, preferably from 0 to 6. The remainder of any carbon atompositions on the Y group are filled by hydrogens.

Y is can be a group including, but not limited to:

or a mixture thereof. Preferably, L is 1 or 2, with the Y groups beingseparated by a moiety selected from R¹ and R² analogs (preferablyalkylene or alkenylene) having from 1 to about 22 carbon atoms and twofree carbon single bonds when L is 2. Z is a water soluble anion, suchas a halide, sulfate, methylsulfate, hydroxide, or nitrate anion,particularly preferred being chloride, bromide, iodide, sulfate ormethyl sulfate anions, in a number to give electrical neutrality of thecationic component.

Amphoteric Surfactants

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be any of anionic or cationic groups described herein forother types of surfactants. A basic nitrogen and an acidic carboxylategroup are the typical functional groups employed as the basic and acidichydrophilic groups. In a few surfactants, sulfonate, sulfate,phosphonate or phosphate provide the negative charge.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphato, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989), which is herein incorporated by reference in its entirety. Thefirst class includes acyl/dialkyl ethylenediamine derivatives (e.g.2-alkyl hydroxyethyl imidazoline derivatives) and their salts. Thesecond class includes N-alkylamino acids and their salts. Someamphoteric surfactants can be envisioned as fitting into both classes.

Amphoteric surfactants can be synthesized by methods known to those ofskill in the art. For example, 2-alkyl hydroxyethyl imidazoline issynthesized by condensation and ring closure of a long chain carboxylicacid (or a derivative) with dialkyl ethylenediamine. Commercialamphoteric surfactants are derivatized by subsequent hydrolysis andring-opening of the imidazoline ring by alkylation—for example withchloroacetic acid or ethyl acetate. During alkylation, one or twocarboxy-alkyl groups react to form a tertiary amine and an ether linkagewith differing alkylating agents yielding different tertiary amines.

Long chain imidazole derivatives which can be used in the compositionsgenerally have the general formula:

wherein R is an acyclic hydrophobic group containing from about 8 to 18carbon atoms and M is a cation to neutralize the charge of the anion,generally sodium. Commercially prominent imidazoline-derived amphotericsthat can be employed in the present compositions include for example:Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate,Cocoamphocarboxy-glycinate, Cocoamphopropyl-sulfonate, andCocoamphocarboxy-propionic acid. Amphocarboxylic acids can be producedfrom fatty imidazolines in which the dicarboxylic acid functionality ofthe amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

The carboxymethylated compounds (glycinates) described herein abovefrequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants.

Long chain N-alkylamino acids are readily prepared by reaction RNH₂, inwhich R═C₈-C₁₈ straight or branched chain alkyl, fatty amines withhalogenated carboxylic acids. Alkylation of the primary amino groups ofan amino acid leads to secondary and tertiary amines. Alkyl substituentsmay have additional amino groups that provide more than one reactivenitrogen center. Most commercial N-alkylamine acids are alkylderivatives of beta-alanine or beta-N(2-carboxyethyl) alanine. Examplesof commercial N-alkylamino acid ampholytes having application in thisinvention include alkyl beta-amino dipropionates, RN(C₂H₄COOM)₂ andRNHC₂H₄COOM. In an embodiment, R can be an acyclic hydrophobic groupcontaining from about 8 to about 18 carbon atoms, and M is a cation toneutralize the charge of the anion.

Suitable amphoteric surfactants include those derived from coconutproducts such as coconut oil or coconut fatty acid. Additional suitablecoconut derived surfactants include as part of their structure anethylenediamine moiety, an alkanolamide moiety, an amino acid moiety,e.g., glycine, or a combination thereof; and an aliphatic substituent offrom about 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can alsobe considered an alkyl amphodicarboxylic acid. These amphotericsurfactants can include chemical structures represented as:C₁₂-alkyl-C(O)—NH—CH₂—CH₂—N⁺(CH₂—CH₂—CO₂Na)₂—CH₂—CH₂—OH orC₁₂-alkyl-C(O)—N(H)—CH₂—CH₂—N⁺(CH₂—CO₂Na)₂—CH₂—CH₂—OH. Disodiumcocoampho dipropionate is one suitable amphoteric surfactant and iscommercially available under the tradename Miranol™ from SolvayNovecare, Princeton, N.J. Another suitable coconut derived amphotericsurfactant with the chemical name disodium cocoampho diacetate is soldunder the tradename Mirataine™, also from Solvay Novecare, Princeton,N.J.

A typical listing of amphoteric classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated by reference in theirentirety.

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionics generally contain cationic and anionic groups which ionizeto a nearly equal degree in the isoelectric region of the molecule andwhich can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate.

Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein. A general formula for these compounds is:

wherein R¹ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from0 to 1 glyceryl moiety; Y is selected from the group consisting ofnitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfuratom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene orhydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Zis a radical selected from the group consisting of carboxylate,sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed aboveinclude:4-[N,N-di(2-hydroxyethyl)-N-octadecylaonio]-butane-1-carboxylate;5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate;3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate;3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;4-1N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammoniol-butane-1-carboxylate;3-1S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfoniol-propane-1-phosphate;3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; andS[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.The alkyl groups contained in said detergent surfactants can be straightor branched and saturated or unsaturated.

The zwitterionic surfactant suitable for use in the present compositionsincludes a betaine of the general structure:

These surfactant betaines typically do not exhibit strong cationic oranionic characters at pH extremes nor do they show reduced watersolubility in their isoelectric range. Unlike “external” quaternaryammonium salts, betaines are compatible with anionics. Examples ofsuitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄acylamidohexyldiethyl betaine; 4-C₁₄₋₁₆acylmethylamidodiethylammonio-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethylbetaine; andC₁₂₋₁₆ acylmethylamidodimethylbetaine.

Sultaines which may be useful in the compositions include thosecompounds having the formula (R(R¹)₂N⁺ R²SO³⁻, in which R is a C₆-C₁₈hydrocarbyl group, each R¹ is typically independently C₁-C₃ alkyl, e.g.methyl, and R² is a C₁-C₆ hydrocarbyl group, e.g. a C₁-C₃ alkylene orhydroxyalkylene group.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated in their entirety.

Method of Forming the Solidified Surfactant Blend:

This disclosure also provides a method of forming the cleaningcomposition. In one embodiment, the method includes the step ofcombining (1) and (3) and optionally (4) and/or (5), as described above.All combinations of (1)-(4) and all combinations of order of additionare hereby expressly contemplated.

In another embodiment, the method includes the steps of providing analcohol having 12 to 14 carbon atoms, an alkylene oxide, and a sulfatingcomponent. Each of the aforementioned components can be combined in anyorder. The alcohol may be any known in the art that has 12, 13, or 14carbon atoms. More than one alcohol or a mixture of alcohols can beutilized.

In various embodiments, the alcohol is further defined as 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 weightpercent of an alcohol having 8, 10, 12, 14, and/or 16 carbon atoms, each±5 weight percent. In other words, any weight combination of C8-C16alcohols may be utilized. In various embodiments, the alcohol is acombination of C12-C14 alcohols. The method may be free of, or excludeuse of, alcohols having less than 12 or more than 14 carbons atoms. Thealcohol(s) may be linear or branched and all isomers of alcohols having8, 9, 10, 11, 12, 13, 14, 15, or 16 carbon atoms are hereby expresslycontemplated for use. The alkylene oxide may be as described above andmay be, for example, ethylene oxide, propylene oxide, or combinationsthereof. The method may exclude use of propylene oxide. In oneembodiment, the alkylene oxide is ethylene oxide and said step ofalkoxylating is further defined as ethoxylating with 1 to 3 moles ofethylene oxide per 1 mole of the alcohol. The sulfating component may beany known in the including, but not limited to, SO₃ or any sulfatingreagent.

The method also includes the step of alkoxylating the alcohol to form acombination of an ethoxylated alcohol and unreacted alcohol. The step ofalkoxylating may be completed using any method known in the art.Typically, alkoxylation is completed at a temperature of from 100° C. to160° C. and at a pressure of from 20 psig to 100 psig.

The method further includes the step of sulfating the ethoxylatedalcohol and the unreacted alcohol to form (1) and (2) and optionally (3)and/or (4), as described above. The step of sulfating may be completedusing any method known in the art.

Additional Embodiments

In additional embodiments, this disclosure provides a method of forminga solid C12/C14-fatty alcohol+0.6EO-sulfate (Na) surfactant. Forexample, an alcohol ethoxylate can be produced by adding 0.6 mol of EOto a base catalyzed C₁₂₋₁₄ fatty alcohol and then sulfated. Thesulfonation of the fatty alcohol ethoxylate can be done in a state ofart falling film sulfonation reactor at a temperature of 40° C. with amolar ratio of SO3/alcohol ethoxylate of 1.0-1.05 with dry air/SO3containing 5 vol % of SO3. The product can be neutralized afterdegassing with a mixture of caustic soda (50%) and water, calculated toobtain a concentration of approx. 30% active at a temperature of 65° C.,keeping the pH-value in the range of 10-12 to avoid hydrolysis of theproduct. The resulting mixture can be dried by different procedures toobtain the solid surfactant. For example, the product may be dried bystate of art freeze drying to obtain a product with a content of water<1%.

This disclosure also provides a method of forming solid blends ofsurfactants. For example, solid and liquid components can be mixedtogether until homogeneous. Water can then be removed from the solid ineither a vacuum oven, in a conventional oven or by freeze drying. Thematerials can then be ground into a powder in a blade grinder.

Methods of Manufacturing Cleaning Compositions

The solidified surfactant blend can be included in various cleaningcompositions. Preferably, the cleaning compositions are solidcompositions. Suitable solid cleaning compositions, include, but are notlimited to granular and pelletized solid compositions, powders, solidblock compositions, cast solid block compositions, extruded solid blockcomposition, pressed solid compositions, and others. Preferably, thecleaning compositions are pressed solids.

Solid particulate cleaning compositions can be made by merely blendingthe dry solid ingredients in appropriate ratios or agglomerating thematerials in appropriate agglomeration systems. Pelletized materials canbe manufactured by compressing the solid granular or agglomeratedmaterials in appropriate pelletizing equipment to result inappropriately sized pelletized materials. Solid block and cast solidblock materials can be made by introducing into a container either aprehardened block of material or a castable liquid that hardens into asolid block within a container. Preferred containers include disposableplastic containers or water soluble film containers. Other suitablepackaging for the composition includes flexible bags, packets, shrinkwrap, and water soluble film such as polyvinyl alcohol.

The solid cleaning compositions may be formed using a batch orcontinuous mixing system. In an exemplary embodiment, a single- ortwin-screw extruder is used to combine and mix one or more components athigh shear to form a homogeneous mixture. In some embodiments, theprocessing temperature is at or below the melting temperature of thecomponents. The processed mixture may be dispensed from the mixer byforming, casting or other suitable means, whereupon the cleaningcomposition hardens to a solid form. The structure of the matrix may becharacterized according to its hardness, melting point, materialdistribution, crystal structure, and other like properties according toknown methods in the art. Generally, a solid cleaning compositionprocessed according to the method of the invention is substantiallyhomogeneous with regard to the distribution of ingredients throughoutits mass and is dimensionally stable.

In an extrusion process, the liquid and solid components are introducedinto final mixing system and are continuously mixed until the componentsform a substantially homogeneous semi-solid mixture in which thecomponents are distributed throughout its mass. The mixture is thendischarged from the mixing system into, or through, a die or othershaping means. The product is then packaged. In an exemplary embodiment,the formed composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 3 hours. Particularly, theformed composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 2 hours. More particularly, theformed composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 20 minutes.

In a casting process, the liquid and solid components are introducedinto the final mixing system and are continuously mixed until thecomponents form a substantially homogeneous liquid mixture in which thecomponents are distributed throughout its mass. In an exemplaryembodiment, the components are mixed in the mixing system for at leastapproximately 60 seconds. Once the mixing is complete, the product istransferred to a packaging container where solidification takes place.In an exemplary embodiment, the cast composition begins to harden to asolid form in between approximately 1 minute and approximately 3 hours.Particularly, the cast composition begins to harden to a solid form inbetween approximately 1 minute and approximately 2 hours. Moreparticularly, the cast composition begins to harden to a solid form inbetween approximately 1 minute and approximately 20 minutes.

In a pressed solid process, a flowable solid, such as granular solids orother particle solids are combined under pressure. In a pressed solidprocess, flowable solids of the compositions are placed into a form(e.g., a mold or container). The method can include gently pressing theflowable solid in the form to produce the solid cleaning composition.Pressure may be applied by a block machine or a turntable press, or thelike. Pressure may be applied at about 1 to about 3000 psi, about 5 toabout 2500 psi, or about 10 psi to about 2000 psi. As used herein, theterm “psi” or “pounds per square inch” refers to the actual pressureapplied to the flowable solid being pressed and does not refer to thegauge or hydraulic pressure measured at a point in the apparatus doingthe pressing. The method can include a curing step to produce the solidcleaning composition. As referred to herein, an uncured compositionincluding the flowable solid is compressed to provide sufficient surfacecontact between particles making up the flowable solid that the uncuredcomposition will solidify into a stable solid cleaning composition. Asufficient quantity of particles (e.g. granules) in contact with oneanother provides binding of particles to one another effective formaking a stable solid composition. Inclusion of an optional curing stepmay include allowing the pressed solid to solidify for a period of time,such as a few hours, or about 1 day (or longer). In additional aspects,the methods could include vibrating the flowable solid in the form ormold, such as the methods disclosed in U.S. Pat. No. 8,889,048, which isherein incorporated by reference in its entirety.

The use of pressed solids provides numerous benefits over conventionalsolid block or tablet compositions requiring high pressure in a tabletpress, or casting requiring the melting of a composition consumingsignificant amounts of energy, and/or by extrusion requiring expensiveequipment and advanced technical know-how. Pressed solids overcome suchvarious limitations of other solid formulations for which there is aneed for making solid cleaning compositions. Moreover, pressed solidcompositions retain its shape under conditions in which the compositionmay be stored or handled.

By the term “solid”, it is meant that the hardened composition will notflow and will substantially retain its shape under moderate stress orpressure or mere gravity. A solid may be in various forms such as apowder, a flake, a granule, a pellet, a tablet, a lozenge, a puck, abriquette, a brick, a solid block, a unit dose, or another solid formknown to those of skill in the art. The degree of hardness of the solidcast composition and/or a pressed solid composition may range from thatof a fused solid product which is relatively dense and hard, forexample, like concrete, to a consistency characterized as being ahardened paste. In addition, the term “solid” refers to the state of thecleaning composition under the expected conditions of storage and use ofthe solid cleaning composition. In general, it is expected that thecleaning composition will remain in solid form when exposed totemperatures of up to approximately 100° F. and particularly up toapproximately 120° F.

The resulting solid cleaning composition may take forms including, butnot limited to: a cast solid product; an extruded, molded or formedsolid pellet, block, tablet, powder, granule, flake; pressed solid; orthe formed solid can thereafter be ground or formed into a powder,granule, or flake. In an exemplary embodiment, extruded pellet materialsformed by the solidification matrix have a weight of betweenapproximately 50 grams and approximately 250 grams, extruded solidsformed by the composition have a weight of approximately 100 grams orgreater, and solid block detergents formed by the composition have amass of between approximately 1 and approximately 10 kilograms. Thesolid compositions provide for a stabilized source of functionalmaterials. In some embodiments, the solid composition may be dissolved,for example, in an aqueous or other medium, to create a concentratedand/or use solution. The solution may be directed to a storage reservoirfor later use and/or dilution, or may be applied directly to a point ofuse.

The following patents disclose various combinations of solidification,binding and/or hardening agents that can be utilized in the solidcleaning compositions of the present invention. The following U.S.patents are incorporated herein by reference: U.S. Pat. Nos. 7,153,820;7,094,746; 7,087,569; 7,037,886; 6,831,054; 6,730,653; 6,660,707;6,653,266; 6,583,094; 6,410,495; 6,258,765; 6,177,392; 6,156,715;5,858,299; 5,316,688; 5,234,615; 5,198,198; 5,078,301; 4,595,520;4,680,134; RE32,763; and RE32818.

Use solutions can be prepared by dissolving and diluting the solidcleaning compositions. Use solutions have a concentration of activeingredients suitable for the desired cleaning application.

Methods of Using the Cleaning Compositions

The cleaning compositions comprising the solidified surfactant blend canbe used by contacting a surface with the cleaning compositions indissolved form. The methods of use also encompass dispensing thecleaning compositions. Preferably, the cleaning compositions aredispensed in dissolved form. The cleaning compositions can be diluted aspart of the dispensing, before dispensing, after dispensing, or acombination thereof. After dispensing, the cleaning composition cancontact a surface. As described herein, surfaces can comprise a hardsurface, ware, or laundry. Preferably, the cleaning compositions are indissolved and diluted form. In some embodiments, the solid cleaningcompositions can contact a surface and subsequently be dissolved on thesurface with the addition of water. In some embodiments, the solidcleaning compositions can contact a surface in dissolved form and thenbe diluted while in contact with the surface. The methods can furthercomprise rinsing the surface with water before and/or after contact withthe cleaning composition.

Preferably, the cleaning composition comprising the solidifiedsurfactant blend provides substantially similar foam properties to aliquid cleaning composition having the same ingredients.

Examples

Various embodiments of a solid cleaning composition are formed as setforth below along with various comparative compositions.

In various embodiments, the solidified surfactant blend includes aSodium C₁₂₋₁₄ Ether Sulfate (SLES) which is (1) a metal alkyl ethersulfate having the formula:

wherein the First Metal is Na, a is 1, AO is ethylene oxide, x is 1, andy is 11-13. It is known that this (1) metal alkyl ether sulfate includesa mixture of compounds wherein x is various values between 0.1 to 3 andy is various values between 11 and 13.

In various embodiments, the solidified surfactant blend includes SodiumC₁₂₋₁₄ (SLS) which is a (4) metal alkyl sulfate having the formula:

wherein the Second Metal is Na, b is 1 and z is 11-13. It is known thatthis (4) metal alkyl sulfate includes a mixture of compounds wherein zis various values between 11 and 13.

In further embodiments, the solidified surfactant blend includes a solidsurfactant such as Sodium LAS which is sodium dodecylbenzenesulfonate.In further embodiments, various additives are also utilized, as setforth below.

Surfactant blend formulations were prepared according to Table 5A todetermine if the blends would form solidified compositions. This isindicated in Table 5A with the description powder or paste. Thedescriptor “powder” indicates that the formulation formed a solidpowder. The descriptor “paste” indicates that the formulation did notform into a solid. As can be seen in Table 5A the exemplary formulations2-9 each formed powders. Formulation 1 did not form a powder, but was apaste.

TABLE 5A 1 2 3 4 5 6 7 8 9 Detergent Component Sodium C12-14  39.6% 19.8%  28.3%  28.3%  28.3%  24.9%  0.0%  28.3%  24.3% Ether SulfateSodium C₁₂₋₁₄ alkyl  60.4%  80.2%  51.7%  44.7%  44.7%  58.1%  0.0% 21.7%  55.7% Sulfate Sodium LAS 100.0%  33.0%  0.0% Additive ComponentMgO₄ (anhydrous)  0.0%    0.0%  7.0%    7.0%  0.0%  7.0%  3.0% Na₂SO₄(anhydrous)  7.0% Polyethylene Glycol  20.0%  20.0%  20.0%  10.0%  0.0% 10.0%  10.0% MW = 8000 Na₂CO₃  0.8% N₂HCO₃  6.3% Totals 100.0% 100.0%100.0% 100.0% 100.0% 100.0% 100.0% 100.0% 100.0% % Anionic 100.0% 100.0% 80.0%  73.0%  73.0%  83.0% 100.0%  83.0%  80.0% Surfactant PhysicalForm after Paste powder Powder powder powder powder powder powder powderDrying

The SLES and the SLS are typically added as a mixture. In thecompositions of Table 5A, an additional amount SLS and/or an additionalamount of a different solid surfactant may also be added. The totalweight percentages of the SLS, SLES, and solid surfactant are set forthbelow and are inclusive of all amounts present as a mixture plus alladded amounts.

The surfactant blends that formed powders were evaluated to determinefoam stability, as described in detail below, processability, andstability. These were tested against control formulations to assess thecomparative properties. Control 1 was a powder sodium C12-14 sulfate.Control 2 was a paste-form sodium C12-14 ether sulfate. The results ofthis tested are provided below in Table 5B.

Foam Stability Test Procedure:

40 ml of solutions of the surfactant blends (250 ppm active) were addedto 250 ml graduated cylinders and placed in a rotating apparatus. Thegraduated cylinders are rotated at 30 rpm for 4 minutes. Initial foamheight in ml in each graduated cylinder is recorded followed by additionof 2 drops (100 microliters via pipette) of corn oil. The graduatedcylinders are then rotated for 2 minutes at 30 rpm and a new foam heightis recorded. This procedure is repeated until the foam has disappearedas determined visually. The total number of drops of the oil needed tomake the foam visually disappear is recorded as “Drops of Oil” in theTable 5B. Duplicate measurements were performed for all samples and theresults set forth above represent an average of the two measurements.

Total Foam Volume is calculated as follows:

Total Foam Volume=Σ(Individual Foam Heights)−(Number of foam Heights)*40mL

The compositions were also evaluated to determine the powder flowcharacteristics of the material. This was accomplished using aBrookfield Powder Flow tester. The sample compositions were placed in acylindrical cell and compacted under a known stress. The normal stressacting on the column of the composition gradually increases untilfailure occurs and the peak normal stress is recorded. A plot ofunconfined failure strength vs. the consolidated stress allows for acalculation of the flow function (ff). Lower flow function values areindicative of free flowing (non-cohesive) powder. It has been found thatflow function of about 0.4 tends to be cohesive and nonflowable. It ispossible that based on other conditions, e.g., internal friction and1^(st) and 5^(th) consolidation strength, that some embodiments having aflow function (ff) of 0.4 can be flowable; however, typically this hasnot found to be the case. Accordingly, a flow function (ff) less thanabout 0.4 is indicative of a non-cohesive, free flowing powder.Preferably, the solidified surfactant blend has a flow function (ff) ofless than about 0.4, more preferably less than about 0.35, mostpreferably between about 0.15 and about 0.35.

TABLE 5B Control Control 1 2 1 2 3 4 5 6 7 8 9 Physical Form afterpowder paste paste powder Powder powder powder powder powder powderpowder Drying Foam Stability Drops of soil until 9 52 86 24 56 38 30 448 45 54 foam disappears Initial Foam Height 250 250 250 175 250 250 250250 250 250 250 in ml Total Foam Volume 450 2270 1575 450 2365 1320 14001800 305 2292 2292 Flow Function (ff) — — — 0.43 0.19 0.50 0.20 0.200.25 0.26 0.25 CAMSIZER — — — 0.654 0.71 0.682 0.72 — 0.54 0.71 0.76(sphericity) Stability? — — — — n/a n/a n/a No n/a n/a Yes Meetperformance? — — — No n/a Yes n/a Yes n/a n/a Yes Process-able? — — —n/a n/a No n/a Yes n/a n/a Yes

Of the surfactant blend compositions that formed solid powders, it wasfound that formulations 6 and 9 had desired non-cohesive powder flowcharacteristics and were processable in a conventional setting. Whilenot wishing to be bound by a particular theory, it is believed theaddition of PEG improved flowability of the formed powders. Otherscompositions that formed powders, for example, composition 4, were foundto be too cohesive and thus not flowable. While composition 6 wasflowable, it was not thermally stable such that it could be processablein many larger scale commercial processes. It was found the addition ofan alkalinity source to Formulation 9 improved the thermal stability ofthe formulation, such that it exhibited sufficient thermal stability forlarger scale commercial processing.

All combinations of the aforementioned embodiments throughout the entiredisclosure are hereby expressly contemplated in one or more non-limitingembodiments even if such a disclosure is not described verbatim in asingle paragraph or section above. In other words, an expresslycontemplated embodiment may include any one or more elements describedabove selected and combined from any portion of the disclosure. Invarious non-limiting embodiments, all values and ranges of valuesbetween and including the aforementioned values are hereby expresslycontemplated.

One or more of the values described above may vary by ±5%, ±10%, ±15%,±20%, ±25%, etc. Unexpected results may be obtained from each member ofa Markush group independent from all other members. Each member may berelied upon individually and or in combination and provides adequatesupport for specific embodiments within the scope of the appendedclaims. The subject matter of all combinations of independent anddependent claims, both singly and multiply dependent, is hereinexpressly contemplated. The disclosure is illustrative including wordsof description rather than of limitation. Many modifications andvariations of the present disclosure are possible in light of the aboveteachings, and the disclosure may be practiced otherwise than asspecifically described herein.

It is also to be understood that any ranges and subranges relied upon indescribing various embodiments of the present disclosure independentlyand collectively fall within the scope of the appended claims, and areunderstood to describe and contemplate all ranges including whole and/orfractional values therein, even if such values are not expressly writtenherein. One of skill in the art readily recognizes that the enumeratedranges and subranges sufficiently describe and enable variousembodiments of the present disclosure, and such ranges and subranges maybe further delineated into relevant halves, thirds, quarters, fifths,and so on. As just one example, a range “of from 0.1 to 0.9” may befurther delineated into a lower third, i.e. from 0.1 to 0.3, a middlethird, i.e. from 0.4 to 0.6, and an upper third, i.e. from 0.7 to 0.9,which individually and collectively are within the scope of the appendedclaims, and may be relied upon individually and/or collectively andprovide adequate support for specific embodiments within the scope ofthe appended claims. In addition, with respect to the language whichdefines or modifies a range, such as “at least,” “greater than,” “lessthan,” “no more than,” and the like, it is to be understood that suchlanguage includes subranges and/or an upper or lower limit. As anotherexample, a range of “at least 10” inherently includes a subrange of fromat least 10 to 35, a subrange of from at least 10 to 25, a subrange offrom 25 to 35, and so on, and each subrange may be relied uponindividually and/or collectively and provides adequate support forspecific embodiments within the scope of the appended claims. Finally,an individual number within a disclosed range may be relied upon andprovides adequate support for specific embodiments within the scope ofthe appended claims. For example, a range “of from 1 to 9” includesvarious individual integers, such as 3, as well as individual numbersincluding a decimal point (or fraction), such as 4.1, which may berelied upon and provide adequate support for specific embodiments withinthe scope of the appended claims.

What is claimed is:
 1. A solidified surfactant blend comprising; (1) atleast one metal alkyl ether sulfate having the formula:

wherein First Metal is sodium, potassium, magnesium, or calcium, a is 1or 2, AO is ethylene oxide, propylene oxide, or combinations thereof, xis 0.1 to 3, and y is 11 to 13, and (2) a solid surfactant; wherein (1)and (2) are present in a weight ratio of from about 30:70 to about 40:60based on a total weight of said solidified surfactant blend; and whereinsaid solidified surfactant blend has a flow function value of less than0.4 as determined using a Brookfield powder flow tester.
 2. Thesolidified surfactant blend of claim 1, further comprising (3) apolyethylene glycol.
 3. The solidified surfactant blend of claim 1wherein (2) is further defined as (4) at least one metal alkyl sulfatehaving the formula:

wherein Second Metal is sodium, potassium, magnesium, or calcium,wherein b is 1 or 2, and wherein z is 11 to
 13. 4. The solidifiedsurfactant blend of claim 1 further comprising an additive component,wherein (1) and (2) are present in an amount of from 25 to 85 weightpercent based on a total weight of the solidified surfactant blend,wherein said polyethylene glycol is from about 1 to about 20 weightpercent based on a total weight of the solidified surfactant blend, andsaid additive component is present in an amount of from about 15 toabout 70 weight percent based on a total weight of the solidifiedsurfactant blend.
 5. The solidified surfactant blend of claim 3 whereinsaid first metal is sodium, a is 1, AO is ethylene oxide, said secondmetal is sodium, and b is
 1. 6. The solidified surfactant blend of claim5 wherein said metal alkyl ether sulfate is sodium lauryl ether sulfateand said metal alkyl sulfate is sodium lauryl sulfate.
 7. The solidifiedsurfactant blend of claim 6 wherein x is 1 to
 3. 8. The solidifiedsurfactant blend of claim 1 wherein said solidified surfactant blendfurther comprises: (5) a second metal alkyl ether sulfate componenthaving the formula:

wherein Third Metal is sodium, potassium, magnesium, or calcium, c is 1or 2, AO is ethylene oxide, propylene oxide, or combinations thereof, mis 0.1 to 3, and n is 11 to 13, and (6) a second metal alkyl sulfatehaving the formula:

wherein Fourth Metal is sodium, potassium, magnesium, or calcium,wherein d is 1 or 2, and wherein t is 11 to
 13. 9. The solidifiedsurfactant blend of claim 8 wherein about 85 to about 95 weight percentof said solidified surfactant blend is a combination of said (1) metalalkyl ether sulfate and said (4) metal alkyl sulfate wherein each of yand z is 11, and wherein about 5 to about 15 weight percent of saidsolidified surfactant blend is a combination of said (5) second metalalkyl ether sulfate and said (6) second metal alkyl sulfate wherein eachof n and t is
 13. 10. The solidified surfactant blend of claim 8 whereinabout 65 to about 75 weight percent of said solidified surfactant blendis a combination of said (1) metal alkyl ether sulfate and said (4)metal alkyl sulfate wherein each of y and z is 11, and wherein about 25to about 35 weight percent of said solidified surfactant blend is acombination of said (5) second metal alkyl ether sulfate and said (6)second metal alkyl sulfate wherein each of n and t is
 13. 11. Thesolidified surfactant blend of claim 8 that is free of: (1) metal alkylether sulfates wherein y is 10 or less and/or wherein y is 14 orgreater; (4) metal alkyl sulfates wherein z is 10 or less and/or whereinz is 14 or greater; (5) second metal alkyl ether sulfates wherein n is10 or less and/or wherein n is 14 or greater; and (6) second metal alkylsulfates wherein t is 10 or less and/or wherein t is 14 or greater. 12.The solidified surfactant blend of claim 8 that is free of: (1) metalalkyl ether sulfates wherein AO is propylene oxide; and (5) second metalalkyl ether sulfates wherein AO is propylene oxide.
 13. The solidifiedsurfactant blend of claim 1 that is free of an alkyl polyglucoside(APG).
 14. The solidified surfactant blend of claim 1 that is free of anamide.
 15. The solidified surfactant blend of claim 8 wherein ((1) andoptionally (5)) and ((4) and optionally (6)) are present in a weightratio of from abut 30:70 to about 50:50, respectively.
 16. Thesolidified surfactant blend of claim 8 wherein ((1) and optionally (5))and ((4) and optionally (6)) are present in a weight ratio of 30:70±5,respectively.
 17. The solidified surfactant blend of claim 1 whereinsaid solidified surfactant blend further comprises an alkalinity sourcein an amount between about 0.1 and about 15 weight percent based on atotal weight of the solidified surfactant blend.
 18. The solidifiedsurfactant blend of claim 2 wherein the polyethylene glycol has a weightaverage molecular weight of about 8,000 g/mol.
 19. The solidifiedsurfactant blend of claim 1 wherein (2) is chosen from Na LAS (sodiumlinear alkylbenzenesulfonate), sodium lauryl sulfoacetate, Sodium AlphaOlefin sulfonate (C14-16 AOS), disodium lauryl sulfosuccinate, andcombinations thereof.
 20. The solidified surfactant blend of claim 1wherein (2) is an alcohol ethoxylates or EO-PO block copolymer.
 21. Amethod of forming the solidified surfactant blend of claim 1 comprisingthe step of combining the (1) and (2).
 22. A method of forming thesolidified surfactant blend of claim 3 comprising the steps of:providing an alcohol having 12 to 14 carbon atoms, an alkylene oxide,and a sulfating component; alkoxylating the alcohol to form acombination of an alkoxylated alcohol and unreacted alcohol; sulfatingthe alkoxylated alcohol and the unreacted alcohol to form (1) and (4).23. The method of forming the solidified surfactant blend of claim 22wherein the alkylene oxide is ethylene oxide and said step ofalkoxylating is further defined as ethoxylating with 0.4 to 3 moles ofethylene oxide per 1 mole of the alcohol.
 24. The method of forming thesolidified surfactant blend of claim 23 wherein the alcohol is furtherdefined as 90 weight percent of C12 alcohol and 10 weight percent of C14alcohol, each ±5 weight percent.
 25. A solid cleaning compositioncomprising: the solidified surfactant blend of claim
 1. 26. The solidcleaning composition of claim 25, wherein the composition is a manualwarewash composition, a laundry composition, a hard surface cleaningcomposition, or a combination thereof.
 27. The solid cleaningcomposition of claim 26, wherein the solidified surfactant blend ispresent in an amount of between about 0.1 weight percent and about 95weight percent of the solid cleaning composition.
 28. The solid cleaningcomposition of claim 27, wherein the composition is a manual warewashcomposition further comprising an alkalinity source and a builder. 29.The solid cleaning composition of claim 28, wherein the alkalinitysource is present in an amount between about 30 weight percent and about90 weight percent of the solid cleaning composition.
 30. The solidcleaning composition of claim 28, wherein the builder is in an amountbetween about 0.01 weight percent and about 30 weight percent of thesolid cleaning composition.
 31. The solid cleaning composition of claim28, wherein the composition further comprises water in an amount betweenabout 1 weight percent and about 50 weight percent of the solid cleaningcomposition.
 32. The solid cleaning composition of claim 29, wherein thealkalinity source is present in an amount between about 30 weightpercent and about 90 weight percent of the solid cleaning composition;wherein the builder is in an amount between about 0.01 weight percentand about 30 weight percent of the solid cleaning composition; whereinthe solidified surfactant blend is in an amount between 0.01 weightpercent and 50 weight percent of the solid cleaning composition; andwherein the composition further comprises water in an amount betweenabout 1 weight percent and about 50 weight percent of the solid cleaningcomposition.
 33. The solid cleaning composition of claim 26, wherein thecomposition is a laundry composition further comprising an alkalinitysource and a builder.
 34. The solid cleaning composition of claim 33,wherein the alkalinity source is present in an amount between about 30weight percent and about 90 weight percent of the solid cleaningcomposition.
 35. The solid cleaning composition of claim 33, wherein thebuilder is in an amount between about 0 weight percent and about 60weight percent of the solid cleaning composition.
 36. The solid cleaningcomposition of claim 33, wherein the composition further comprises waterin an amount between about 1 weight percent and about 50 weight percentof the solid cleaning composition.
 37. The solid cleaning composition ofclaim 33, wherein the alkalinity source is present in an amount betweenabout 30 weight percent and about 90 weight percent of the solidcleaning composition; wherein the builder is in an amount between about1 weight percent and about 50 weight percent of the solid cleaningcomposition; wherein the solidified surfactant blend is in an amountbetween 0.01 weight percent and 40 weight percent of the solid cleaningcomposition; and wherein the composition further comprises water in anamount between about 0 weight percent and about 60 weight percent of thesolid cleaning composition.
 38. The solid cleaning composition of claim26, wherein the composition is a hard surface cleaning compositionfurther comprising an alkalinity source and a builder.
 39. The solidcleaning composition of claim 38, wherein the alkalinity source ispresent in an amount between about 30 weight percent and about 90 weightpercent of the solid cleaning composition.
 40. The solid cleaningcomposition of claim 38, wherein the builder is in an amount betweenabout 0.01 weight percent and about 30 weight percent of the solidcleaning composition.
 41. The solid cleaning composition of claim 38,wherein the composition further comprises water in an amount betweenabout 0.01 weight percent and about 20 weight percent of the solidcleaning composition.
 42. The solid cleaning composition of claim 38,wherein the alkalinity source is present in an amount between about 30weight percent and about 90 weight percent of the solid cleaningcomposition; wherein the builder is in an amount between about 0.01weight percent and about 30 weight percent of the solidified surfactantblend; wherein the solid detergent component is in an amount between 1weight percent and 20 weight percent of the solid cleaning composition;and wherein the composition further comprises water in an amount betweenabout 0.01 weight percent and about 20 weight percent of the solidcleaning composition.
 43. The solid cleaning composition of claim 29,wherein the alkalinity source comprises an alkali metal hydroxide, analkali metal carbonate, a metal silicate, a metal borate, an alkanolamine, or combinations thereof.
 44. The solid cleaning composition ofclaim 43, wherein the alkalinity source is in an amount sufficient toprovide a pH of between about 7 and about 14 in a use solution.
 45. Thesolid cleaning composition of claim 26, wherein the solid cleaningcomposition provides pH of at least about 5.5.
 46. The solid cleaningcomposition of claim 26 further comprising a cosurfactant comprising anonionic surfactant, a cationic surfactant, an anionic surfactant, asemi-polar nonionic surfactant, an amphoteric surfactant, a zwitterionicsurfactant, or a combination thereof.
 47. The solid cleaning compositionof claim 26, wherein the solid cleaning composition is a granular solid,pelletized solid, cast solid, extruded solid block, or pressed solid.48. The solid cleaning composition of claim 47, wherein the cleaningcomposition is a pressed solid.
 49. The solid cleaning composition ofclaim 26, further comprising at least one of the following additionalingredients an acid source, an activator, an anti-redeposition agent, ableaching agent, a chelating agent, a dye, an odorant, a filler, afunctional polydimethylsiloxone, a hardening agent, a hydratable salt, apolymer, or a sanitizer.
 50. A method of cleaning a surface comprising:contacting the surface with a cleaning composition of claim 25 indissolved form.
 51. The method of claim 50, wherein the cleaningcomposition is further in diluted form.
 52. The method of claim 51,wherein the cleaning composition is diluted from the dissolved form. 53.The method of claim 50, wherein the surface comprises a hard surface,ware, or laundry.
 54. The method of claim 53, further comprising rinsingthe surface with water.
 55. The method of claim 53, wherein the cleaningcomposition provides substantially similar foam properties to a cleaningcomposition having the same ingredients except that the metal alkylether sulfate is a liquid.
 56. A method of dispensing a cleaningcomposition comprising: dispensing the cleaning composition of claim 26in dissolved form; and contacting a surface with the cleaningcomposition.
 57. The method of claim 56, wherein the cleaningcomposition is a powder, a flake, a granule, a pellet, a tablet, alozenge, a puck, a briquette, a brick, a solid block, or a unit dose.58. The method of claim 56, wherein the cleaning composition is dilutedfrom the dissolved form.
 59. The method of claim 56, wherein the surfacecomprises a hard surface, ware, or laundry.
 60. The method of claim 59,further comprising rinsing the surface with water.
 61. The method ofclaim 56, wherein the cleaning composition provides substantiallysimilar foam properties to a cleaning composition having the sameingredients except that the metal alkyl ether sulfate is a liquid.